TW200817477A - Optical information recording medium and azo-metal complx dye - Google Patents
Optical information recording medium and azo-metal complx dye Download PDFInfo
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- TW200817477A TW200817477A TW096136272A TW96136272A TW200817477A TW 200817477 A TW200817477 A TW 200817477A TW 096136272 A TW096136272 A TW 096136272A TW 96136272 A TW96136272 A TW 96136272A TW 200817477 A TW200817477 A TW 200817477A
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
- G11B7/2467—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes azo-dyes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/18—Monoazo compounds containing copper
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/20—Monoazo compounds containing cobalt
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/22—Monoazo compounds containing other metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
- C09B69/04—Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds
- C09B69/045—Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds of anionic azo dyes
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/2407—Tracks or pits; Shape, structure or physical properties thereof
- G11B7/24073—Tracks
- G11B7/24079—Width or depth
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds
- G11B7/2495—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds as anions
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
- G11B7/0045—Recording
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/256—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers improving adhesion between layers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
- G11B7/266—Sputtering or spin-coating layers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
200817477 25795pif.doc 九、發明說明: • 【發明所屬之技術領域】 • 本發明是關於一種可利用雷射光進行資訊記錄及再生 之光資afu己錄媒體以及财光性極為優異之偶氮金屬錯合物 染料,例如本發明是關於對使用波長小於等於440 nm的 短波長雷射光來記錄及再生資訊為合適的加熱模式(heat mode)型光資訊記錄媒體以及適合用於光資訊記錄媒體的 記錄層之偶氮金屬錯合物染料。 ( 【先前技術】 最近,網際網路(internet )等網路及高晝質電視 (Hi-Vision TV)正迅速地普及。另外,隨著高畫質電視 (High Definition Television,HDTV)播放的臨近,對於 用以經濟簡便地記錄圖像資訊之大容量記錄媒體的要求亦 在增加。上述可錄光碟(Compact Disk Recordable , CD_R) 以及可將可見雷射光(630 nm〜680 nm)作為記錄用雷射 光進行高密度記錄之可錄型數位影音光碟(Digital vide〇 (:Disk-Recordable,DVD-R),可確保某種程度作為大容量記 錄媒體的地位,但並不具有可滿足將來所要求的充分大的 口己錄谷畺。因此’業界正在進行藉由使用波長短於Dvd_r 的短波長的雷射光來提鬲記錄密度、從而具備更大記錄容 量之光碟的開發,例如提供一種使用405 nm藍色雷射之 所謂Blu-ray (藍光)方式光記錄碟片。 以往,於DVD-R型光碟中,作為記錄層中所含有之 染料化合物,一直是有利地使用偶氮金屬錯合物染料(例 6 200817477 25795pif.doc • 3 專利特開平n—31。728號公報、日本專利特開 7〇旒公報、日本專利特開2002 —274040號公 ' 利特開168237號公報)。這些偶氮金屬 ::如:厂ΐ有與紅色雷射對應的吸收波形,對於405 nm 射田土:而舌亚非較好。因此,於使用405 nm的藍色雷 、之光記錄磁碟(〇ptical rec〇r d 的錢金屬錯合物騎了⑽波長的短 ( 、自、研九,公開有日本專利特開2001 —158862號公 日利特開細6— 142789號公報、日本專利特開 2_1_7G號公報、日本專利特開屬—29號公 相士日本專利特開2005 — 297407號公報等。然而,這些公 ㈣載的技術,雖然揭示了染料溶液或染料膜的最大 ⑽,但並未充分記載耐光性及光資訊記錄媒體中之 :二、,特性的詳細内容’因而對實際的保存性及記錄再 生特性並不瞭解。 ^ 對於上述日本專利特開麵—158862號公報、日本專 。卢八Γ纖―142789號公報、日本專利特開2_ —3_70 二2二本專觸開聰―29屬號公報、日本專利特 i膜的^9·7號公報中所記載之偶氮金屬錯合物,對染 錄再峰2性、以及對應藍色雷射的光資訊記錄媒體的記 .己錚ΐΓΐ订了評價,結果並未發現可同時滿足耐光性 …錄再生将性(記錄靈敏度、2TCNR)。 【發明内容】 本發明是鑒於上述課題而完成,其目的在於提供一種 7 200817477 25795pif.doc 顯示具有良好的溶解性、良好的記錄再生特性、且 高的耐光性之光資訊記錄媒體(尤复H /、有極 、尤其疋能夠利用波長小於 荨於440 nm的雷射絲射進行資訊記錄之光資訊媒 體)以及可製造此光資訊記錄媒體ϋ 、 a y、 丄。 之偶虱金屬錯合物染料。 本查明之其他目的在於提供—種耐光性極優異、且執 穩定性優異之偶氮金屬錯合物染料。 …、 本發明中,藉由選擇特定的偶氮染料以及合成方法, 而獲得陰離子性偶氮金屬錯合物。關於陽離子性、中性、 以及陰離子性偶氮金屬錯合物,若魏独金屬離子及配 位基所形成的鍵,則_般認為,因按照陽離子性〈中性〈 陰離子性_序共賴性高的_數量增加,故金屬離子 的配位場***(ligand fleld splitting)增大(參昭講談社 Scientific,新版錯合物化學,基礎錯合物工學研究會ς, 30頁〜42頁)。另外,以金屬離子及配位基所形成二環, =牙螯合物(bidentate ehelate)的情形下以5員環最為 穩定(麥照講談社Scientific,新版錯合物化學,基礎錯二 學研究會編,84頁),因此認為若2個以3牙的“ 朵料(配位基)及金屬離子所形成的環的兩個環均形成、$ ^環,^存在金屬離子與偶氮染料(配位基)的鍵結會變 付更加牢固、金屬離子的配位場***變大的可能性。由= ,為,「偶氮配位基的π—π*躍遷」與「金屬離子的d〜〆 躍遷」之間的相互作用變大。一般認為,其結果會高效宏 地引起自金屬離子的d—d*躍遷狀態之能量失活過二二 而提高染料的耐光性。 攸 8 200817477 25795pif.doc 本發明者們基於上述思考進行了努 如下見解:特定的陰離子性偶氮金屬錯合物毕料 極為,光性、良好的溶解性、優異具: 而獲付如下見解:藉由將本發明之偶氮金: 於記錄層,而使利用小於等於44〇顏的藍色用 冗錄再生之光資訊記錄媒體獲得良好的記錄再生特性w f 若===明之偶氮金屬錯合物染料的合成條件下, :使k式(1-1)或通式(1—2)於鹼性條件下盥全 二H ’則生成與上述偶氮金屬錯合物相比金屬離 數I較多之偶氮金屬錯合物。 其中,發現尤其是金屬離子與偶氮染料配位基之 比二的偶氮金屬錯合物,與上述偶氮金屬錯合物相比”,、、 ΐ不有較好的耐光性、較好的記錄再生特性。藉此,盘先 ^佳使用的Co離子及Ni離子相比,使用Cu離子謂 ::二?己錄性能兩方面均更為優異之光資訊記錄媒 奴,f獲件新的見解,基於此見解而達成本發明。 藉由以下構成而較好地達成本發明之課題。 •[]本卷月之光資訊記錄媒體,為具有含有軌距(track Ptch為如〜500 _的預刻溝槽(师抑晴)的基板、 ,/、有可藉由知射小於等於44〇 nm的雷射光而進行資訊 ^,的。己錄層之光資訊記錄媒體;其特徵在於··上述記錄 、九含有至^、種偶氮金屬錯合物染料,該偶氮金屬錯合物 =是由=下述通式(1_υ或通式(1_2)表示的偶氮 木辟所獲*之2價偶氮染料陰離子及金屬離子_成。其 9 200817477 中,通式(1 — 1)或通式(1 一2)具有可解離成Q的氫原 子,此氫原子與下述通式(1 一 1)或通式(1一2)中以* 表示的-NH-基的氫原子同時解離而與金屬離子結合,藉此 獲得此偶氮金屬錯合物染料。此偶氮金屬錯合物染料亦可 含有除通式(1 — 1)、通式(1— 2)及金屬離子以外的成分。 (卜 1) (1-2)200817477 25795pif.doc IX. Description of the invention: • [Technical field to which the invention pertains] The present invention relates to an optical recording material that can be used for information recording and reproduction using laser light, and an azo metal which is excellent in optical properties. Compound dye, for example, the present invention relates to a heat mode type optical information recording medium suitable for recording and reproducing information using short-wavelength laser light having a wavelength of 440 nm or less and a recording suitable for use in an optical information recording medium. Layer of azo metal complex dye. ([Prior Art] Recently, Internet and high-definition televisions (Hi-Vision TVs) are rapidly spreading. In addition, as high-definition television (HDTV) playback approaches There is also an increasing demand for large-capacity recording media for economical and easy recording of image information. The above-mentioned Compact Disk Recordable (CD_R) and visible laser light (630 nm to 680 nm) can be used as a recording mine. Digital vide (: Disk-Recordable, DVD-R), which is capable of high-density recording, ensures a certain degree of status as a large-capacity recording medium, but does not have the ability to meet future requirements. A large enough port has been recorded. Therefore, the industry is developing the use of short-wavelength laser light with a wavelength shorter than Dvd_r to increase the recording density and thus have a larger recording capacity, for example, to provide a 405 nm. The so-called Blu-ray optical recording disc of the blue laser. In the past, in the DVD-R type optical disc, as the dye compound contained in the recording layer, there has been The use of an azo metal complex dye (Example 6 200817477 25795 pif. doc • 3 Patent Laid-Open No. 31-728, Japanese Patent Laid-Open Publication No. 7-Jia, Japanese Patent Laid-Open No. 2002-274040) Japanese Patent No. 168237). These azo metals: such as: the plant has an absorption waveform corresponding to the red laser, for the 405 nm field soil: and the tongue is not good. Therefore, using a blue mine of 405 nm, The light recording disk (〇ptical rec〇rd's money metal complex rides a short (10) wavelength (,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Japanese Patent Laid-Open No. Hei 2_1_7G, Japanese Patent Laid-Open No. 29, Japanese Laid-Open Patent Publication No. 2005-297407, etc. However, these public (four)-loaded techniques disclose dye solutions or dye films. Maximum (10), but does not adequately describe the light resistance and optical information recording media: Second, the details of the characteristics 'Therefore, the actual preservation and recording and reproduction characteristics are not known. ^ For the above-mentioned Japanese patent special opening -158862 Bulletin Japanese special. Lu Ba Yi fiber - 142789 bulletin, Japanese patent special opening 2_ - 3_70 22nd special contact with Kai Cong-29 genus bulletin, Japanese patent special film, No. 9·7 bulletin The nitrogen metal complex, which has been evaluated for the dyeing and re-peaking, and the optical information recording medium corresponding to the blue laser, has not been found to satisfy the light resistance at the same time. Record sensitivity, 2TCNR). SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a light information recording medium which exhibits good solubility, good recording and reproducing characteristics, and high light resistance (Ultra H). /, extremely, especially, can use the laser light source with a wavelength less than 440 nm for information recording) and can manufacture this optical information recording medium 、, ay, 丄. Even the ruthenium metal complex dye. The other object of the present invention is to provide an azo metal complex dye which is excellent in light resistance and excellent in stability. In the present invention, an anionic azo metal complex is obtained by selecting a specific azo dye and a synthesis method. Regarding cationic, neutral, and anionic azo metal complexes, if a bond formed by a single metal ion and a ligand is present, it is considered to be based on the cationic <neutral < anionic The high number of _ increases, so the ligand flel splitting of metal ions increases (School, Scientific, New Edition of Complex Chemistry, Foundational Complex Engineering Research Society, 30-42) . In addition, the formation of a bicyclic ring with a metal ion and a ligand, and a five-membered ring is most stable in the case of a bidentate ehelate (Mr. Nirvana Scientific, a new version of the compound chemistry, a basic two-study study) Edited, 84 pages), it is considered that if two rings of a ring formed by three teeth "codons (ligands) and metal ions are formed, $^ ring, ^ there are metal ions and azo dyes ( The bond of the ligand) will become stronger and the possibility of the metal field coordination field splitting becomes larger. From =, is, "the π-π* transition of the azo ligand" and the "metal ion d" The interaction between ~〆〆迁” has become larger. It is generally believed that the result is highly efficient in inducing the energy inactivation from the d-d* transition state of the metal ion to increase the light resistance of the dye.攸8 200817477 25795pif.doc The present inventors have made the following observations based on the above considerations: the specific anionic azo metal complex is extremely diverse, light, good solubility, excellent: and the following insights are obtained: By using the azo gold of the present invention in the recording layer, a blue recording and reproducing medium having a reproducible light is obtained by using a blue light of 44 or less. If the azo metal is wrong, the azo metal is wrong. Under the synthesis conditions of the dye, the k formula (1-1) or the general formula (1-2) is subjected to bismuth all H' under alkaline conditions to form a metal divisor compared with the above azo metal complex. I have more azo metal complexes. Among them, it has been found that, in particular, the azo metal complex of the ratio of the metal ion to the azo dye ligand is inferior to the above azo metal complex, and has no good light resistance. The recording and reproducing characteristics of the disc are better than those of the Co ion and the Ni ion, and the Cu ion is said to be: the second recording performance is superior to the optical information recording medium slave, f is new The present invention has been achieved based on the above findings. The subject matter of the present invention is preferably achieved by the following configuration: • [] This month's light information recording medium has a track gauge (track Ptch is as ~500 _ The substrate of the pre-groove (Shen-Yi-Ying), and/or the optical information recording medium capable of performing information by detecting laser light of 44 〇 nm or less; - the above-mentioned record, nine-containing, azo-metal complex dyes, which are obtained from azo ash, which is represented by the following formula (1_υ or formula (1_2)* a divalent azo dye anion and a metal ion _ ing. In its 9 200817477, the formula (1 - 1) or the formula ( 1 to 2) having a hydrogen atom dissociable into Q, which is simultaneously dissociated from a hydrogen atom of the -NH- group represented by * in the following general formula (1 - 1) or (1 - 2) The azo metal complex dye is obtained by combining metal ions. The azo metal complex dye may also contain components other than the general formula (1-1), the general formula (1-2), and a metal ion. (卜1) (1-2)
通式(1一 1)以及通式(1 一2)中,Q表示碳環基或雜 環基,R6〜R8各自獨立表示氫原子或取代基。 [2]如[1]所述之光資訊記錄媒體,其中上述記錄層含有 至少一種以下述通式(A)表示的偶氮金屬錯合物染料。 通式(A) (L2_)n(L’)m(MV(Xp+)k, 通式(A)中,ΐΛ表示藉由使下述通式(1 一 1)或通 式(1 一2)中所含有的2個氫原子解離而獲得之2價偶氮 染料陰離子,Lf表示配位基,Μ表示金屬離子(包含金屬 氧化物離子),η表示1〜4範圍内的整數,m表示0〜3範 圍内的整數,r表示1或2,Xp+為p價陽離子,p表示1 〜10範圍内的整數,k’是在0<k’$4的範圍内、表示通式 (A)中的負電荷除以p之値。 10 200817477 25795pif.doc (Η) (1-2)In the formula (1 - 1) and the formula (1 - 2), Q represents a carbocyclic group or a heterocyclic group, and R6 to R8 each independently represent a hydrogen atom or a substituent. [2] The optical information recording medium according to [1], wherein the recording layer contains at least one azo metal complex dye represented by the following formula (A). General formula (A) (L2_)n(L')m(MV(Xp+)k, in the general formula (A), ΐΛ represents the following general formula (1 - 1) or general formula (1 - 2) A divalent azo dye anion obtained by dissociating two hydrogen atoms contained therein, Lf represents a ligand, Μ represents a metal ion (including a metal oxide ion), η represents an integer in the range of 1 to 4, and m represents 0. An integer in the range of ~3, r represents 1 or 2, Xp+ is a p-valent cation, p represents an integer in the range of 1 to 10, and k' is in the range of 0 <k'$4, representing the formula (A) The negative charge is divided by the number of p. 10 200817477 25795pif.doc (Η) (1-2)
通式(1 — 1)以及通式(1 — 2)中,Q表示碳環基或 雜環基。R6〜R8各自獨立表示氳原子或者取代基。 [3]如[2]所述之光資訊記錄媒體,其中上述偶氮金屬錯 合物染料是以下述通式(2—1)表示之偶氮金屬錯合物染 料。 通式(2— 1 )In the formula (1 - 1) and the formula (1-2), Q represents a carbocyclic group or a heterocyclic group. R6 to R8 each independently represent a ruthenium atom or a substituent. [3] The optical information recording medium according to [2], wherein the azo metal complex dye is an azo metal complex dye represented by the following formula (2-1). General formula (2 - 1)
(χΡ+)πΒ 通式(2—1)中,Μ表示金屬離子(包含金屬氧化物 離子),Q2表示形成雜環的原子群。L1表示配位基。Χρ+ 為Ρ價陽離子,Ρ表示1〜10範圍内的整數,q表示1〜4 範圍内的整數。nl表示1或2,n2表示0〜3的整數,n3 是在0<n3$4的範圍内,表示以q/p算出之值。R6、R7 各自獨立表示氫原子或者取代基。 [4]如[2]所述之光資訊記錄媒體,其中上述偶氮金屬錯 11 200817477 25795pif.doc 合物染料為以下述通式(3— 1)表示的偶氮金屬錯合物染 料。 通式(3— 1 )(χΡ+)πΒ In the formula (2-1), Μ represents a metal ion (including a metal oxide ion), and Q2 represents a group of atoms forming a hetero ring. L1 represents a ligand. Χρ+ is a valence cation, Ρ represents an integer in the range of 1 to 10, and q represents an integer in the range of 1 to 4. Nl represents 1 or 2, n2 represents an integer of 0 to 3, and n3 is in the range of 0 < n3$4, and represents a value calculated by q/p. R6 and R7 each independently represent a hydrogen atom or a substituent. [4] The optical information recording medium according to [2], wherein the azo metal complex dye is an azo metal complex dye represented by the following general formula (3-1). General formula (3 - 1)
(χΡ+)η3 通式(3—1)中,Μ表示金屬離子(包含金屬氧化物 離子),Q2表示形成雜環的原子群。L1表示配位基。Χρ+ 為Ρ價陽離子,Ρ表示1〜10範圍内的整數,q表示1〜4。 nl表示1或2,n2表示0〜3的整數,n3是在0<n3$4 的範圍内、表示以q/p算出之值。R6、R8各自獨立表示氫 原子或者取代基。(χΡ+)η3 In the formula (3-1), Μ represents a metal ion (including a metal oxide ion), and Q2 represents a group of atoms forming a hetero ring. L1 represents a ligand. Χρ+ is a valence cation, Ρ represents an integer in the range of 1 to 10, and q represents 1 to 4. Nl represents 1 or 2, n2 represents an integer of 0 to 3, and n3 represents a value calculated by q/p in the range of 0 < n3$4. R6 and R8 each independently represent a hydrogen atom or a substituent.
[5]如[1]所述之光資訊記錄媒體,其中上述偶氮金屬錯 合物染料,是使下述通式(1 一 1)或通式(1 一2)中所含 有的2個氳原子解離而獲得的2價偶氮染料陰離子與金屬 離子之數量比為1比1或者金屬離子數量較多之化合物。[5] The optical information recording medium according to [1], wherein the azo metal complex dye is two of the following formula (1 - 1) or formula (1 - 2) A compound having a ratio of a divalent azo dye anion to a metal ion obtained by dissociating a ruthenium atom is 1 to 1 or a large amount of a metal ion.
12 20081747712 200817477
中,Q表示碳環基或 離子之數量比為4比5之化合物。 [6]如⑴所述之光資訊記錄媒體,其中上述^氮金屬錯 合物染料,是使下述通式(1 —υ或通式(1—2)中所含 有的2個氫原子解離而獲得的2價偶氮染料陰離子與金屬In the formula, Q represents a compound having a carbocyclic group or an ion ratio of 4 to 5. [6] The optical information recording medium according to (1), wherein the above-mentioned nitrogen metal complex dye dissociates two hydrogen atoms contained in the following formula (1 - hydrazine or in the formula (1-2) And the obtained divalent azo dye anion and metal
通式(1一 1)以及通式(1一2)中,Q表示碳環基或 雜環基,R6〜R8各自獨立表示氳原子或者取代基。 [7]如[5]所述之光賀s己錄媒體’其中以下述通式(β ) 來表示上述偶氮金屬錯合物染料。 通式(B) (L2-)s(L2)t(M)u-(Yv〇w 通式(B)中,L2$示使下述通式或通式(1 〜2)中所含有的2個氫原子解離而獲得的2價偶氮染料陰 離子,L2表示配位基,V[表示金屬離子(包含金屬氧化物 離子),s表示1〜4範圍内的整數,t表示〇〜14範圍内的 整數’ u表示2〜5的整數,γν_為v價陰離子,v表示1〜 比範圍内的整數,w是在〇<w^4的範圍内、表示通式(Β) 中的正電荷除以v之值。 13 200817477 25795pif.doc (1 一 ί) (1-2)In the formula (1 - 1) and the formula (1 - 2), Q represents a carbocyclic group or a heterocyclic group, and R6 to R8 each independently represent a halogen atom or a substituent. [7] The photoreported media described in [5] wherein the above azo metal complex dye is represented by the following formula (β). (B) (L2-)s(L2)t(M)u-(Yv〇w In the formula (B), L2$ is represented by the following formula or formula (1 to 2) A divalent azo dye anion obtained by dissociating two hydrogen atoms, L2 represents a ligand, V [ represents a metal ion (including a metal oxide ion), s represents an integer in the range of 1 to 4, and t represents a range of 〇 14 The integer 'u' in the integer represents an integer of 2 to 5, γν_ is a v-valent anion, v represents an integer in the range of 1 to 4, and w is in the range of 〇<w^4, which represents the formula (Β) The positive charge is divided by the value of v. 13 200817477 25795pif.doc (1 a ί) (1-2)
通式(1一1)以及通式(1 一2)中,Q表示碳環基或 雜環基,R6〜R8各自獨立表示氫原子或者取代基。 [8] 如[2]至[4]中任一項所述之光資訊記錄媒體,其中 上述Xp+為銨陽離子(ammonium cation )。 [9] 如[1]、[5]、[6]或[7]所述之光資訊記錄媒體,其中 上述金屬離子為銅離子。 [10] 如[1]至[9]中任一項所述之光資訊記錄媒體,其中 在具有軌距為50 nm〜500 nm的預刻溝槽的基板之具有預 刻溝的面上依序積層有反射層、記錄層。 [11] 本發明之偶氮金屬錯合物染料,其特徵在於:其 是以下述通式(C)來表示。 通式(C) (Cu2+)5(L2-)4]2+(Yv')fw 通式(C)中,1^2_表示使下述通式(1一 1)或通式(1 —2)中所含有的2個氫原子解離而獲得的2價偶氮染料陰 離子,(γν% 表示(cr)2、(B〇2、(Γ)2、(C1CV)2、(PF6〇2、 (BF4_)2、S042·、(CH3COO_)2 中的任一陰離子。 14 200817477 25795pif.doc CM) Rs N k-N 酬 ¥ 1-1In the general formula (1 - 1) and the general formula (1 - 2), Q represents a carbocyclic group or a heterocyclic group, and R6 to R8 each independently represent a hydrogen atom or a substituent. [8] The optical information recording medium according to any one of [2] to [4] wherein the Xp+ is an ammonium cation. [9] The optical information recording medium according to [1], [5], [6] or [7] wherein the metal ion is copper ion. [10] The optical information recording medium according to any one of [1] to [9] wherein the pre-grooved surface of the pre-grooved substrate having a gauge of 50 nm to 500 nm is The sequential layer has a reflective layer and a recording layer. [11] The azo metal complex dye of the present invention is characterized by the following formula (C). Formula (C) (Cu2+)5(L2-)4]2+(Yv')fw In the formula (C), 1^2_ means that the following formula (1 -1) or formula (1) 2) A divalent azo dye anion obtained by dissociating two hydrogen atoms contained in (a), (γν% represents (cr)2, (B〇2, (Γ)2, (C1CV)2, (PF6〇2) Any of the (BF4_)2, S042·, (CH3COO_)2. 14 200817477 25795pif.doc CM) Rs N kN ¥¥1
(1-2) R6 N(1-2) R6 N
N N HN. Q,nN N HN. Q,n
I 通式(1一 1)以及通式(1 一2)中,Q表示經取代或 未經取代的吡唑(pyraz〇le)環基。R6〜R8各自獨立表示 經取代或未經取代的烷基或者經取代或未經取代的芳基。 如以上說明,根據本發明之光資訊記錄媒體,可藉由 於記錄層中使用本發明之偶氮金屬錯合物染料,而製造顯 示具有良好的記錄再生特性、且具有極高的耐光性之光資 訊記錄媒體(尤其是可利用波長小於等於440 nm的雷射 光照射進行資訊記錄之光資訊記錄媒體)。 士田2本發明之偶氮金屬錯合物染料,亦可應用於照 :声/多鏟^吸收材料、彩色據光片(C〇1〇rfllter)用染 熱轉印記錄材料,^ 可進一步瞭解上述二:::::佳實施形態例的說明’ 【實施方式】 、目的、特徵以及優點。 以下,就本發明之来次4二 物染料加以詳細說明。貝㈣錄媒體以及偶氮金屬錯合 本發明之光資訊記錄 進行資訊記錄之記錄層,基板上具有至少一廣; 層、保護層。 軚子的疋進一步設置有光反射 15 200817477 25795pif.doc 定的^^光資訊記錄媒體的記錄層,是由至少一種特 疋的偶虱金屬錯合物染料而構成。 ㈣ί本發明之偶氮金屬錯合物染料加以說明。本 金屬錯合物染料,是指藉由使上述通式(卜υ 氮i屬錯合物 金屬離子在一定條件下反應而獲得之偶In the formula (1 - 1) and the formula (1 - 2), Q represents a substituted or unsubstituted pyrazol ring group. R6 to R8 each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. As described above, according to the optical information recording medium of the present invention, light having excellent recording and reproducing characteristics and having high light resistance can be produced by using the azo metal complex dye of the present invention in the recording layer. Information recording media (especially optical information recording media that can be used for information recording by laser light having a wavelength of 440 nm or less). Shitian 2 The azo metal complex dye of the invention can also be applied to the photo-acoustic/multi-shovel absorbing material, the color light-receiving sheet (C〇1〇rfllter), and the thermal transfer recording material, Understand the above two::::: Description of the preferred embodiment [Embodiment], purpose, features and advantages. Hereinafter, the next four dyes of the present invention will be described in detail. Bay (4) Recording Media and Azo Metal Mismatch The optical information recording of the present invention has a recording layer for information recording, and the substrate has at least one wide layer; a protective layer. The cymbal of the cymbal is further provided with light reflection 15 200817477 25795pif.doc The recording layer of the optical recording medium is composed of at least one characteristic bismuth metal complex dye. (d) The azo metal complex dye of the present invention is described. The metal complex dye refers to an even one obtained by reacting a metal ion of the above formula (diazepine nitrogen complex) under certain conditions.
沾通式(1-1)或通式(1^2)具有可解離成Q 此氫原子與下述通式(丨叫)或通式(1-2) 合^此氯原子同時解離,而與金屬離子結 :L女二人二偶^屬錯合物染料。而減金屬錯合物染 :二t除通式(卜1)、通式(h2)以及金屬離子以 外的成分。 —使通式(1-1)或通式(卜2)與金屬離子反應時的 疋if、件,疋指於反應系統中至少含有驗。作為驗,只要 是可合成上述偶氮金屬錯合物染料的鹼即可,並無特別限 定。作為此種驗’例如可舉出:烧基胺(alkylamine)(例 如,二乙胺(triethylamine)、乙二胺(ethylenediamine)、 嗎淋(morpholine )、吡嗪(pyrazine )等)、芳胺(㈣咖―)、 脒(amidine)(例如,1;8_二氮雜雙環[54〇]十一碳_7•烯 (l,8_diaZabiCyCl〇[5.4.0]-undec_7_ene,DBU)等)、胍 (guanidine)、含氮芳香族雜環(例如,吼啶(pyridine)、 咪唑(imidazole )等)、無機鹼(例如,乙酸按(amm〇nium acetate)、碳酸氫鈉、碳酸鈉、氫氧化鈉、碳酸鉀、氫氧化 鉀、氨(ammonia)等)。 16 200817477 25795pif.doc “Q中所含有的可解離的氫原子,,夕讲邮「 是指^果成為解離謙卩可, 產生解離転度的pKa (酸解離常數彳 、、瓜 於20,更好的是小於等於15 ^,較好的是小於等 對於除通式ο-υ、通式(更^疋小於等於10。 的成分並無特別限^ ’其例如可舉出.2金屬離子以外 …,出·反應溶劑、鹼、除 述的配位基。 外—料、以及後The dipping formula (1-1) or the formula (1^2) has dissociable into Q, and the hydrogen atom is simultaneously dissociated from the chlorine atom of the following formula (bark) or formula (1-2), and And metal ion knot: L female two people two even ^ is a complex dye. The metal-reducing compound is dyed: two components except the formula (Bu 1), the formula (h2), and the metal ion. - The 疋if, member, 疋 when the general formula (1-1) or the general formula (b) is reacted with a metal ion means at least the test in the reaction system. The test is not particularly limited as long as it is a base which can synthesize the above azo metal complex dye. As such an examination, for example, an alkylamine (for example, triethylamine, ethylenediamine, morpholine, pyrazine, etc.) or an aromatic amine (for example) may be mentioned. (4) coffee-), amidine (amidine) (for example, 1;8-diazabicyclo[54〇]undec-7_ene (l,8_diaZabiCyCl〇[5.4.0]-undec_7_ene, DBU), etc.), 胍(guanidine), nitrogen-containing aromatic heterocyclic ring (for example, pyridine, imidazole, etc.), inorganic base (for example, acetic acid (amm〇nium acetate), sodium hydrogencarbonate, sodium carbonate, sodium hydroxide , potassium carbonate, potassium hydroxide, ammonia (ammonia), etc.). 16 200817477 25795pif.doc "The dissociable hydrogen atom contained in Q," is said to be a dissociation of pKa (acid dissociation constant 彳, melon 20, more Preferably, it is 15 ^ or less, preferably less than or equal to the formula ο-υ, and the formula (more than 10 is less than or equal to 10), which may be, for example, a metal ion other than .2 ..., the reaction solvent, the base, the ligand described above, the external material, and the
作為上述金屬離子(金屬氣化物離 例如可舉出:錢(Mg)、IS (Α1) ^金屬離子), (SC)、鈦(το、飢⑺、路( = s;)、娜)、銳 姑(Co)、鎳(Ni)、銅(〇1)、鋅(2 ) ’ =η)鐵(Fe)、 砷㈤、,剩、纪⑺、錯心 錄㈤、釕⑽、姥⑽、楚(Pd)、^(Ag)、、^^ 銦(In)、錫(Sn)、銻(Sb)、鋇(b ) ’’ 镱⑽、給⑽、钽叫鶴心:=^^^ 銀(Ir)、始(Pt)、金(Au)、|(H)、於 e 鐵⑻、 秘(Bi)、钍(Th)等的金屬離子,、二(T1),(Pb)、 原子的離子。賴過渡金>1原子Λ彡二㈣疋過渡金屬 族〜廳元妙及Ib、具衫«表的❿ 义王α电子層之元辛。對於 過渡金屬原子,,定’但較好⑽Examples of the metal ion (metal vaporization include: money (Mg), IS (Α1) ^ metal ion), (SC), titanium (το, hun (7), road (= s;), Na), sharp Gu (Co), Nickel (Ni), Copper (〇1), Zinc (2) ' = η) Iron (Fe), Arsenic (5), Remaining, Ji (7), Mistakes (5), 钌 (10), 姥 (10), Chu (Pd), ^(Ag), ^^ Indium (In), tin (Sn), bismuth (Sb), 钡(b) '' 镱(10), give (10), 钽叫鹤心:=^^^ Silver ( Ir), initial (Pt), gold (Au), |(H), metal ions such as e iron (8), secret (Bi), ruthenium (Th), etc., two (T1), (Pb), atomic ions . Lai transition gold > 1 atomic Λ彡 two (four) 疋 transition metal family ~ Hall Yuan Miao and Ib, with a shirt « table 义 Yi Wang α electronic layer of Yuan Xin. For transition metal atoms, it is better but better (10)
NiTzFn:;r、Pd、Ir,、Re,_RNiTzFn:;r, Pd, Ir, Re, _R
Cr、Mn'Fe'a>'Nl'c:u、Zn,更較好 c〇、Ni、Cu、Zn,^^^、c〇、Ni、Cu。 17 200817477 25795pif.doc 為2 Γ/Λ 較好的是2價或3價的金屬原子。作 金屬(以金屬離子表示),例如可舉出: R 1 ;/Γ、C〇2+、C〇3+、Ni2+、Ni3+、、 F ' ;3+' Rrh ; Pd2+'Ir3+' R2+' Re+ # ^ Mn- ^Cr, Mn'Fe'a> 'Nl'c: u, Zn, more preferably c〇, Ni, Cu, Zn, ^^^, c〇, Ni, Cu. 17 200817477 25795pif.doc is 2 Γ / Λ It is preferably a divalent or trivalent metal atom. As a metal (indicated by metal ions), for example, R 1 ; /Γ, C〇2+, C〇3+, Ni2+, Ni3+, F'; 3+' Rrh; Pd2+'Ir3+' R2+' Re+ # ^ Mn- ^
Fe、F:、c〇、c〇3+m、z 是 M、c〇2+、c〇3+、Np、Cu2+、Zn2 t = 是 Fe2+、Co2+、C〇3+、Ni2+、Ni3+、r”2+ + 更季乂好的 严料人骗、、九別 Cu 。本發明之偶氮金Fe, F:, c〇, c〇3+m, z are M, c〇2+, c〇3+, Np, Cu2+, Zn2 t = Fe2+, Co2+, C〇3+, Ni2+, Ni3+, r 2+ + 更 更 更 更 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 。 。 。
(·; 屬錯5物乐料,就耐光性以及記錄再生特性 尤其好的是α^。 ’ 另外,光資訊記錄媒體中之偶氮金屬錯合物,就财光 性之*觀點而言,與㈣隹子相比,較好的是選擇见離子及 離子f但是,就環境危害性以及對人體的毒性方面而 吕丄與沁離子或Co離子相比,較好的是Cu離子;使用 有告性低的金屬離子(例如Cu離子、Zn離子或離子), 在光資訊記錄媒體以及染料的擴大銷售方面有較大意義。 現就通式(丨一1)或(1一2)加以說明。R6〜R8各自 獨立8表示氫原子或取代基。就提高溶解性之觀點而言,R6 〜^較好的是取代基。對於以R6〜R8所表示的取代基並 無特別限定,制如可舉出:自素原子、烧基(包含環烷 基、雙環烷基)、烯基(包含環烯基、雙環烯基)、炔基 (alkynyl)方基(aryl )、雜環基(heter0CyC]jc group )、 氛基(cyano group)、羥基、硝基、羧基、烷氧基、芳氧基、 矽氧基(silyloxy)、雜環氧基、醯氧基(acyl〇xy)、胺甲醯 基氧基(carbamoyloxy)、烷氧基羰基氧基、芳氧基羰基氧 18 200817477 25795pif.doc 基、胺基(包含苯胺基(anilino))、醯基胺基(acylamin〇)、 • 胺基羰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、胺石黃 - 醯基胺基(sulfam〇ylamino)、烷基及芳基磺醯基胺基、疏 基(thiol)、烧硫基(alkylthio)、芳硫基、雜環硫基、胺石黃 醯基、磺基(sulfo group)、烷基及芳基亞磺醯基(aryl sulfmyl)、烷基及芳基績醯基、醯基、芳氧基羰基、烷氧 基羰基、胺甲醯基(carbamoyl)、芳基及雜環偶氮基、醯 亞胺基(imido)、膦基(phosphino )、氧膦基(ph〇sphinyl)、 C 磷氧基(PhosPhinyi〇xy)、氧膦基胺基、矽烷基(siiyD。 更詳細而言,R6〜R8表示鹵素原子(例如氯原子、溴 原子、碘原子)、烷基[表示直鏈、支鏈、環狀的經取代或 未經取代的烧基,上述烧基,包含烧基(較好的是碳數工 〜30的烷基,例如甲基、乙基、正丙基、異丙基、第三丁 基、正辛基、二十烷基(eicosyl)、2'氯乙基、2_氰基乙基、 2-乙基己基)、環烷基(較好的是碳數3〜3〇的經取代或未 經取代的環烷基,例如環己基、環戊基、‘正十二烷基環 I 己基)雙知、纟元基(較好的是碳數5〜30的經取代或未經取 代的雙環烷基,即自碳數5〜30的雙環烷烴(bicycl〇alkane) 中去掉1個氫原子的1價基。例如雙環[122]庚烷_2_基、 雙環[2·2·2]辛烧各基)、進而亦包含環結構較多的三環結構 專以下說明的取代基中的烧基(例如烧硫基中的燒基) 亦表示此種概念的烷基]、烯基[表示直鏈、支鏈、環^的 經取代或未經取代的烯基;上述烯基,包含烯基(較好的 是碳數2〜30的經取代或未經取代的烯基,例如乙烯基 19 200817477 25795pif.doc fmyl)、缔丙基(allyl)、異戊二稀 _基(較好的是碳數二 、 ° 、'二取代的環烯基,即去掉碳數3〜30的環嫌 ^個If子的1價基毫 曰土二;;_基(經取代或未經取代的雙環烯基,較 撞且:Γ個錐〜30的經取代或未經取代的雙環烯基,即去 卓ς有個X鍵的雙環稀烴中的u(·; It is a faulty material, and it is particularly good in light resistance and recording and reproducing characteristics. ' In addition, the azo metal complex in the optical information recording medium is in terms of the fiscal property*. Compared with (4) scorpion, it is better to choose ions and ions. However, in terms of environmental hazard and toxicity to human body, it is better to use Cu ion than strontium ion or Co ion; Low metal ions (such as Cu ions, Zn ions, or ions) have great significance in the expansion of optical information recording media and dyes. Now, the general formula (丨1) or (1-12) is explained. R6 to R8 each independently represent a hydrogen atom or a substituent. From the viewpoint of improving solubility, R6 is preferably a substituent. The substituent represented by R6 to R8 is not particularly limited. There may be mentioned a self atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group, a bicycloalkenyl group), an alkynyl group (aryl), and a heterocyclic group (heter0CyC). ]jc group ), cyano group, hydroxyl, nitro, carboxyl, alkoxy, Oxyl, silyloxy, heterocyclic oxy, acyl xy, carbamoyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy 18 200817477 25795pif. Doc group, amine group (including anilino), acylamin(R), • aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, amine stone yellow-fluorenyl group Sulfamylylamino, alkyl and arylsulfonylamino, thiol, alkylthio, arylthio, heterocyclic thio, amine sulfonyl, sulfo group ), alkyl and aryl sulfmyl, alkyl and aryl fluorenyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl and hetero Cyclo azo, imido, phosphino, ph〇sphinyl, C phosphorus oxy (PhosPhinyi 〇 xy), phosphinylamino group, decyl group (siiyD. In detail, R6 to R8 represent a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom), an alkyl group [indicating a linear, branched, cyclic substituted or unsubstituted The alkyl group, the above-mentioned alkyl group, comprising a burning group (preferably an alkyl group having a carbon number of -30, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, Eicosyl, 2'chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl (preferably substituted or unsubstituted carbon 3 to 3 fluorene) a cycloalkyl group, such as a cyclohexyl group, a cyclopentyl group, a 'n-dodecylcyclohexyl group, a di-, a fluorenyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms), That is, a monovalent group of one hydrogen atom is removed from a bicycloalkane (bicycl〇alkane) having 5 to 30 carbon atoms. For example, a bicyclo[122]heptane-2-yl group, a bicyclo[2·2·2] octyl group, and a tricyclic structure having a large number of ring structures, and a substituent in the substituents described below (for example, burning) The alkyl group in the thio group also represents the alkyl], alkenyl group of the concept [is a straight-chain, branched, cyclic substituted or unsubstituted alkenyl group; the above alkenyl group, containing an alkenyl group (preferably Is a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as vinyl 19 200817477 25795 pif.doc fmyl), allyl, isoprene-based (preferably carbon number 2) , °, 'disubstituted cycloalkenyl group, that is, the monovalent silane of the ring if the carbon number is 3 to 30 is removed; the _ group (substituted or unsubstituted dicycloalkenyl group) Collision: a substituted or unsubstituted bicycloalkenyl group of ~30 cones, ie, u in a bicyclic hydrocarbon with an X bond
如雙環阳]庚姊^、雙環 ^基例 咖2〜3。的經取代或未經取2 美乙炔炔丙基(卿al>gy1)、三甲基矽烷 U較好的是碳數6〜30的經取代或未經取 如苯基、對甲苯基(p购υ、萘基(naphthyi)、 間虱本基 '鄰十W基胺基苯基—Ο 雜縣(較㈣是自5或6員的經取代或未經取 ^的θ域非芳麵雜環化合物中去除丨個氫原子的工 賈基’更好的是碳數3〜3G的5或6員的芳香族雜環基; =如,2-吱喃基(2_furyl)、2_嗟吩基(2_thienyi)、2_π密啶 基(2-pyrhnidinyD、2_笨幷噻唑基(2_benz〇thiaz〇iyi))、 齓基、羥基、硝基、羧基、烷氧基(較好的是碳數1〜30 的經取代或未經取代的垸氧基,例如甲氧基、乙氧基、異 =氧基、第三丁氧基、正辛氧基、2_甲氧基乙氧基)、芳氧 土(較好的疋’石反數6〜3〇的經取代或未經取代的芳氧基, 例如苯氧基(phenoxy)、2_甲基苯氧基、4_第三丁基苯氧 基、3_硝絲氧基、2什四醯基胺絲氧基)、魏氧^(較 20 200817477 25795pif.doc 好的是碳數3〜20的矽烷氧基,例如三甲基矽烷氧基、第 二丁基二甲基矽氧基)、雜環氧基(較好的是碳數2〜30 _ 的f取代或未經取代的雜環氧基、1-苯基四唑-5-氧基、2- 51 b 南基氧基(2_tetrahydr〇pyranyl〇Xy))、醯氧基(較 好的疋曱fe氧基(formyl〇xy)、碳數2〜3〇的經取代或未 經取代的垸基絲氧基、碳數6〜3〇的經取代或未經取代 白j芳基幾基氧基,例如㈣氧基、乙醯氧基、三甲基乙酸 ξ ,土( Ρ·νΜ〇Υΐ〇χΥ )、硬脂醯氧基(stearoyloxy )、苯甲酿 1 氧基㈤nZ〇yl〇Xy)、對甲氧基苯基羰基氧基)、胺甲醯氧 基(杈好的是碳數1〜30的經取代或未經取代的胺甲酸氧 基,例如N,队二甲基胺甲酿氧基、N,N-二乙基胺甲醯氧 基、嗎魏縣氧基、即_二_正辛基胺基錄氧基、n_ 正辛基胺甲酿氧基)、烧氧基幾氧基(較好的是石炭數2〜30 雜取代或核取代的_基縣氧基,例如甲氧基絲 氧,、乙基氧基、第三丁氧基幾基氧基、正辛基幾 基氧基)、芳氧基幾基氧基(較好的是石炭數7〜30的經取代 I或未經取代的芳氧基幾基氧基,例如苯氧基魏基氧基、對 甲氧基苯氧基幾基氧基、對正十六烧基氧基苯氧基幾基氧 基)、胺基(較好的是胺基、碳數1〜30的經取代或未經取 代的烧基絲、碳數6〜3G驗取代或未縣代的苯胺 j,例=二胺基、二甲胺基、苯胺基、N_甲基_苯胺 土、一本基胺基)、醯胺基(較好的是,甲醯胺基、碳數工 二30的經取倾未經取代的絲錄絲、碳數Μ 、、二取代或未',工取代的芳基幾基胺基,例如甲醯胺基、乙酿 21 200817477 25795pif.doc 細基、二甲基乙酿胺基、月桂酿胺基、苯曱酿胺基、3 4 5-三-正辛氧基苯基羰基胺基)、胺基羰基胺基(較好的是碳 數1〜30的經取代或未經取代的胺基羰基胺基,例如胺曱 酉&基胺基、N,N-一甲基胺基幾基胺基、N,N-二乙基胺基幾 基胺基、嗎啉基羰基胺基)、烷氧基羰基胺基(較好的是碳 數2〜30的經取代或未經取代的烷氧基羰基胺基,例如甲 氧基羰基胺基、乙氧基羰基胺基、第三丁氧基羰基胺基、 正十八烷氧基羰基胺基、N-甲基-曱氧基羰基胺基)、芳氧 基魏基胺基(較好的是碳數7〜30的經取代或未經取代的 芳氧基羰基胺基,例如苯氧基羰基胺基、對氯苯氧基羰基 胺基、間正辛氧基苯氧基羰基胺基)、胺磺醯基胺基二 的是碳數〇〜30的經取代或未經取代的胺磺醯基胺基,例 如胺磺醯基胺基、N,N-二曱基胺基磺醯基胺基、N_正辛基 胺基磺醯基胺基)、烷基及芳基磺醯基胺基(較好的是碳^ 1〜30的經取代或未經取代的烷基績醯基胺基、碳數6〜3〇 的經取代或未經取代的絲_基胺基,例如?基續酿基 胺基、丁基磺醯基胺基、苯基磺醯基胺基、2,3,5_三氣苯^ 石黃醯基胺基、對甲絲基魏基胺基)、、院硫基(ς 好的是碳數1〜30的經取代或未經取代触硫基,例如甲 硫基、乙硫基、正十六綠硫基)、芳絲(缺的是碳數 6〜30的娜代絲脉代料絲,例 苯硫基、間曱氧基苯硫基)、雜環硫基(較好的是碳數t 30的經取代或未經取代的雜環硫基,例如2_苯幷嗔唾炉 基、1-苯基时5·基硫基)、胺俩基(較好的是碳數= 22 200817477 25795pif.doc 〜30的經取代或未經取代的胺磺醯基,例如n_乙基胺磺 醢基N-(3-十—烷基氧基丙基)胺磺酿基、耶-二甲基胺 石黃酿基、N·乙酿基胺顧基、N•苯甲酿基胺績醯基、n_(象 苯基胺甲酿基)胺顧基)、奴、域及芳基亞雜基(較 好的是碳數1〜30的經取代或未經取代的絲亞橫酿基、 碳數=〜30的經取代或未經取代的芳基亞雜基,例如甲 基亞%醯基、乙基亞磺醯基、苯基亞磺醯基、對曱基苯基 亞磧醯基)、絲及芳基顧基(較好的是碳數卜抑的經 取代或未經取代的絲輕基、碳數6〜3()的經取代或未 經取代的芳基磺醯基,例如甲基石黃酸基、乙基石黃醯基、苯 基磺《、對甲基苯基雜基)、酿基(較好的是甲醯基、 礙數2〜30的經取代或未經取代的絲祕、碳數7〜3〇 的經取代或未經取代的芳基羰基、碳數4〜3〇的經取代或 未經取代的碳原子與縣結合_環羰基,例如乙醯基、 一甲基乙S&基、2-氯乙醯基、硬脂醯基、苯甲醯基、對正 辛基氧基苯基m基、2音域絲、2士綠絲)、芳氧 基幾基(較好的是碳數7〜30的經取代絲經取代的芳氧 基叛基’例如苯氧基幾基、鄰氯苯氧基幾基、間硝基苯氧 基%基、對第三丁基苯氧基羰基)、烷氧基羰基(較好的是 石反數2〜30的經取代或未經取代的烧氧基幾基,例如甲氧 基%基、乙氧基魏基、第三丁氧基Μ基、正十人炫基氧基 叛基)、胺曱醯基(較好的是,碳數丨〜孙的經取代或未經 取代的胺甲酸基,例如胺甲酸基、Ν_曱基胺曱醯基、ν,ν_ 一曱基胺甲醯基、Ν,Ν_二-正辛基胺曱醯基、Ν_(曱基續醯 200817477 25795pif.doc 基)胺曱醯基)、4 的經取代或未‘2,偶氮基(較好的是碳數6〜30 或未經取代的;=的,偶氮基、碳數3〜30的經取代 氮基々乙基石户其^^基,例如苯基偶氮基、對氯苯基偶 好的是N 丁 _ 1 ’ ’4>^塞一唑基偶氮基)、醯亞胺基(較 基,例如二=Γ : _取代或未經取代的膦Such as double ring yang] Geng 姊 ^, double ring ^ base case coffee 2 ~ 3. Substituted or unsubstituted 2 acetylene propargyl (clear al > gy1), trimethyl decane U is preferably a substituted or unsubstituted phenyl or p-tolyl group having a carbon number of 6 to 30. Buy 萘, naphthyi, 虱 虱 ' 邻 邻 W W W W ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( More preferably, the working group in which the hydrogen atom is removed from the ring compound is a 5- or 6-membered aromatic heterocyclic group having a carbon number of 3 to 3 G; =, for example, 2-furyl, 2_porphine (2_thienyi), 2_π-midridinyl (2-pyrhnidinyD, 2_benz〇thiaz〇iyi), fluorenyl, hydroxy, nitro, carboxyl, alkoxy (preferably carbon number 1) ~30 substituted or unsubstituted methoxy group, such as methoxy, ethoxy, iso-oxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), aromatic Oxygen (a preferred substituted or unsubstituted aryloxy group of 6' to 3', such as phenoxy, 2-methylphenoxy, 4-tert-butylbenzene Oxyl, 3-nitroxyloxy, 2-tetradecylamine-siloxy), Wei-oxygen (more than 20 200 817477 25795pif.doc is preferably a decyloxy group having a carbon number of 3 to 20, such as a trimethylnonyloxy group, a second butyldimethyloxy group, or a heterocyclic oxy group (preferably, a carbon number of 2 to 2). 30 _ of f-substituted or unsubstituted heterocyclic oxy, 1-phenyltetrazole-5-oxy, 2- 51 b-andyloxy (2_tetrahydr〇pyranyl〇Xy), decyloxy (preferably) a substituted or unsubstituted fluorenylmethyloxy group having a carbon number of 2 to 3 fluorene, a substituted or unsubstituted white aryl group having a carbon number of 6 to 3 fluorene Alkoxy group, for example, (tetra)oxy, ethoxylated, trimethylglycolate, earth (Ρ·νΜ〇Υΐ〇χΥ), stearyloxy, benzoic acid (5) nZ〇yl〇 Xy), p-methoxyphenylcarbonyloxy), amine methoxycarbonyl (preferably substituted or unsubstituted carboxylic acid oxy group having a carbon number of 1 to 30, such as N, dimethylamine A methoxy, N,N-diethylamine methyl methoxy, weiwei oxy, ie _di-n-octylamine oxy, n-n-octylamine methoxy, oxygenated Alkoxy group (preferably a charcoal number 2 to 30 hetero- or nuclear-substituted _ group An oxy group, such as methoxymethylox, ethyloxy, a third butoxyoxy, n-octyloxy, or an aryloxyoxy group (preferably a charcoal number) 7 to 30 substituted I or unsubstituted aryloxymethyloxy groups, such as phenoxyweiyloxy, p-methoxyphenoxyoxy, p-hexadecanoyloxybenzene An oxymethyloxy group, an amine group (preferably an amine group, a substituted or unsubstituted alkyl group having a carbon number of 1 to 30, a carbon number of 6 to 3 G, or an aniline j of no county). Examples = diamino, dimethylamino, anilino, N-methyl-aniline, a radical amino group, amidino (preferably, amidoxime, carbon number two 30) An unsubstituted silk-recorded silk, carbon number 、, disubstituted or unsubstituted aryl arylamino group, such as formazanyl, ethyl broth 21 200817477 25795pif.doc fine base, dimethyl Ethylamine, lauric acid, benzoguanamine, 3 4 5-tri-n-octyloxycarbonylcarbonyl), aminocarbonylamino group (preferably having a carbon number of 1 to 30) Substituted or unsubstituted aminocarbonylamino group, such as amine hydrazine &Amino, N,N-monomethylaminomethyl, N,N-diethylaminoamino, morpholinylcarbonylamino), alkoxycarbonylamino Preferred are substituted or unsubstituted alkoxycarbonylamino groups having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, or Alkoxycarbonylamino, N-methyl-nonyloxycarbonylamino), aryloxy-Wilylamine (preferably substituted or unsubstituted aryloxycarbonylamine having 7 to 30 carbon atoms) a group such as a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, a m-octyloxyphenoxycarbonylamino group, an amine sulfonylamino group, a substituted carbon number of 〇30 or Unsubstituted amine sulfonylamino group, such as sulfonylamino, N,N-didecylaminosulfonylamino, N-n-octylaminosulfonylamino), alkyl And an arylsulfonylamino group (preferably a substituted or unsubstituted alkyl fluorenylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted filament having a carbon number of 6 to 3 Å) Amino group, for example? Retinoylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trisylbenzene, sulphate, p-methyl-Wilylamine, Sulfur-based (ς is a substituted or unsubstituted thiol group having a carbon number of 1 to 30, such as methylthio, ethylthio, n-hexadecylthio), and an aromatic filament (the missing carbon number is 6~) 30 纳代丝脉代丝,为phenylthio, m-decyloxyphenylthio), heterocyclic thio (preferably a substituted or unsubstituted heterocyclic thio group having a carbon number t 30, For example, 2_benzoquinone furnace base, 1-phenyl group 5·ylthio group), amine 2 group (preferably carbon number = 22 200817477 25795 pif.doc ~ 30 of substituted or unsubstituted amine sulfonate Sulfhydryl group, for example, n-ethylaminesulfonyl N-(3-deca-oxypropyl)amine sulfonate, yttrium-dimethylamine sulphate, N-ethylamine , N•Benzyl amide, n_(like phenylamine), amine, sulfonyl, and arylidene (preferably substituted with 1 to 30 carbon atoms) Unsubstituted or unsubstituted arylheteroylene, such as methyl, having a carbon number = 〜30 % mercapto, ethylsulfinyl, phenylsulfinyl, p-nonylphenyl fluorenylene, silk and aryl benzyl (preferably carbon number substituted or not) Substituted silk light group, substituted or unsubstituted arylsulfonyl group having 6 to 3 carbon atoms, such as methyllithenic acid, ethyl sulphate, phenyl sulfonyl, p-methylphenyl Base), a thiol group (preferably a fluorenyl group, a substituted or unsubstituted filament of 2 to 30, a substituted or unsubstituted arylcarbonyl group having a carbon number of 7 to 3 Å, a carbon number 4 to 3 〇 of a substituted or unsubstituted carbon atom bonded to a county _ ring carbonyl group, such as ethyl hydrazino, monomethyl s S & base, 2-chloroethyl fluorenyl, stearyl sulfhydryl, benzhydryl , p-octyloxyphenyl m-group, 2-sound filament, 2 s green wire), aryloxy group (preferably substituted alkyl substituted aryloxy group with carbon number 7~30) For example, a phenoxy group, an o-chlorophenoxy group, a m-nitrophenoxy group, a p-tert-butylphenoxycarbonyl group, an alkoxycarbonyl group (preferably a stone inverse number of 2 to 30) Substituted or unsubstituted alkoxy group, For example, methoxy-based, ethoxy- Wei-ki, tert-butoxy-decyl, n-decanoyloxy, and amine-based (preferably, carbon number 丨~sun) Or unsubstituted urethane groups, such as urethane groups, Ν 曱 曱醯 曱醯 、, ν, ν 曱 曱 胺 胺 Ν Ν, Ν, Ν 二 二 正 正 曱醯 Ν Ν (曱基醯200817477 25795pif.doc yl) amidino), 4 substituted or not '2, azo (preferably carbon number 6~30 or unsubstituted; =, azo The substituted nitrogen group 々 ethyl ketone having a carbon number of 3 to 30, such as a phenyl azo group or a p-chlorophenyl group, is preferably N 丁 1 ' '4> 塞 oxazolyl azo Alkyl group, a quinone imine group (more than a base, such as a ruthenium: _substituted or unsubstituted phosphine
膦基(較好膦基、?基苯氧基膦基)、氧 ♦疋厌數2〜30經的取代或未經取代的氧膦 =箕乳膦基、二辛基氧基氧膦基、二乙基氧基氧麟基)、 ’牛虱土(較好的是碳數2〜3〇的經取代或未經取代的磷氧 例如二笨基氧基膦氧基、二辛基氧基碟氧基)、氧膦基 ,基(較好的是碳數2〜3〇的經取代或未經取代的氧膦基 胺基,例如二甲氧基氧膦基胺基、二甲胺基氧膦基胺基)、 石夕烧基(較好的是碳數3〜3〇的經取代或未經取代的石夕烧 基,例如三甲基矽烷基、第三丁基二曱基矽烷基、苯基二 曱基矽烷基)。 上述的官能基’亦可將具有氳原子的官能基除去,進 而被上述基團取代。作為此種官能基的例子,可例舉出: 烧基幾基胺基磺醢基、芳基幾基胺基績酿基、烧基續酸基 月女基#炭基、芳基石黃酿基胺基幾基。作為其例,可舉出··甲 基石Kiife基胺基幾基、對甲基本基石頁酸基胺基幾基、乙酸胺 基磺醯基、苯甲醯基胺基磺醯基。 R6,較好的是碳數1〜1〇的經取代或未經取代的烷 基、碳數6〜20的經取代或未經取代的芳基、碳數1〜10 24 200817477 25795pif.doc 的經取代或未經取代的烷氧基、碳數6〜20的經取代或未 經取代的方氧基、碳數2〜10的經取代或未經取代的醢 基、碳數2〜1〇的經取代或未經取代的烷氧基羰基、碳數 1〜10的經取代或未經取代的烷基磺醯基;更好的是碳數1 〜8的經取代或未經取代的烧基、碳數$〜15的經取代或 未經取代的芳基;更較好的是碳數1〜6的經取代或未經取a substituted or unsubstituted phosphine oxide having a phosphino group (preferably a phosphino group, a phenoxyphosphinyl group), an oxygen oxime, an anthraquinone, an unsubstituted phosphinyl group, a fluorenylphosphine group, a dioctyloxyphosphinyl group, Diethyloxy oxanyl), 'burdock earth (preferably substituted or unsubstituted phosphorus such as diphenyloxyphosphinooxy, dioctyloxy having 2 to 3 carbon atoms) Alkoxy), phosphinyl, benzyl (preferably a substituted or unsubstituted phosphinylamino group having a carbon number of 2 to 3 Å, such as dimethoxy phosphinylamino, dimethylamino a phosphinylamino group, a sulfonyl group (preferably a substituted or unsubstituted fluorene group having a carbon number of 3 to 3 Å, such as a trimethyl decyl group, a third butyl decyl decane Base, phenyl fluorenyl decyl). The above functional group ' may also remove a functional group having a halogen atom and be substituted by the above group. Examples of such a functional group include, for example, an alkylaminosulfonyl group, an arylmethylamine group, a calcined acid group, a carbon group, and an aryl stone base. Amino groups. Examples thereof include a methyl group Kiifeylamino group, a p-methyl sulfenylamino group, an aminoacetic acid sulfonyl group, and a benzhydrylaminosulfonyl group. R6, preferably a substituted or unsubstituted alkyl group having 1 to 1 carbon number, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a carbon number of 1 to 10 24 200817477 25795 pif.doc a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted fluorenyl group having 2 to 10 carbon atoms, and a carbon number of 2 to 1 Å a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms; more preferably a substituted or unsubstituted carbon having a carbon number of 1 to 8. a substituted or unsubstituted aryl group having a carbon number of from $15 to 15; more preferably a substituted or unsubstituted carbon number of from 1 to 6
代的烷基。烷基中,較好的是碳數3〜6的支鏈烷基,更好 的是碳數4〜6的第三烷基。 3較好的是,R7或R8為取代基。作為取代基,較好的 疋石厌數1〜ίο的經取代或未經取代的烷基、碳數6〜2〇的 經取代絲錄代的芳基;更好的是碳數丨〜6的經取 未經取代的烷基。 ^ 长本實施形態之以通式(H)或通式(1-2)表示的 ,氮木料,僅€載有偶氮_腙(hydraz_)互變異構性 衡(tautomeric equilibrium)中的偶氮型,但亦可為對應 ,型’此時_型與本實施形態所記載之錢型是同二成 Q表示魏基或㈣基。其巾 ::基上具有與金屬離子共價結合的原子。二= 具有與金屬離子結合的原子時,具 土上 個氫原子解離而與金屬離子共料 1含的— 個氯原子解離而與金屬離子共^使― 出:經基、絲、絲、絲、亀:絲例如可舉 作為Q的取代基上具有與金屬離子結合的原子時,鱼 25 200817477 25795pif.docAlkenyl. The alkyl group is preferably a branched alkyl group having 3 to 6 carbon atoms, more preferably a third alkyl group having 4 to 6 carbon atoms. Preferably, R7 or R8 is a substituent. As a substituent, a preferred substituted or unsubstituted alkyl group having 1 to ί of anthraquinone, a substituted alkyl group having 6 to 2 carbon atoms; more preferably a carbon number 丨~6 The unsubstituted alkyl group is taken. ^ In the long embodiment, the nitrogen wood, represented by the general formula (H) or the general formula (1-2), contains only the azo in the azo-hydrazide tautomeric equilibrium. The type may be a corresponding type, and the type described in this embodiment is the same as the money type described in the embodiment, and represents a Wei group or a (four) group. Its towel has an atom on its base which is covalently bonded to a metal ion. 2 = When there is an atom bonded to a metal ion, the hydrogen atom on the soil dissociates and the chlorine ion contained in the metal ion conglomerate 1 dissociates from the metal ion to form a crystal, silk, silk, and silk.亀: silk can be exemplified as having an atom bonded to a metal ion on the substituent of Q, fish 25 200817477 25795pif.doc
金屬離子共價結合之取代基’較好的是輕基、胺基(較好 的是胺基、碳數1〜30的經取代或未經取代的烷基胺基、 碳數6〜30的經取代或未經取代的苯胺基,例如胺基、甲 胺基、二甲胺基、苯胺基、N-甲基·苯胺基、二苯基胺基)、 酿胺基(較好的是甲醯胺基、碳數1〜30的經取代或未經 取代的烧基羰基胺基、碳數6〜30的經取代或未經取代的 芳基羰基胺基,例如曱醯胺基、乙醯基、三甲基乙醯基胺 基、月桂醯胺基、苯甲醯基胺基、3,4,5_三_正辛氧基苯基 幾基胺基)、胺基幾基胺基(較好的是碳數1〜3〇的經取代 或未經取代的胺基幾基胺基,例如胺甲酿基胺基、N,n_二 甲基胺基羰基胺基、N,N-二乙基胺基羰基胺基、嗎啉基羰 基胺基)、烷氧基羰基胺基(較好的是碳數2〜3〇的經取代 或未經取代的烷氧基羰基胺基,例如甲氧基羰基胺基、乙 氧基羰基胺基、第三丁氧基羰基胺基、正十八烷氧基羰基 胺基、N-甲基-甲氧基羰基胺基)、芳氧基羰基胺基(較好 的是碳數7〜30的經取代絲經取代的純基録胺基, j如苯氧基羰基胺基、對氣苯氧基羰基胺基、間正辛氧基 苯氧基%基胺基)、胺磺醯基胺基(較好的是碳數〇〜孙 =經取代絲姆代__基絲,例如胺磺酿基胺 ς、Ν,Ν_:曱基胺基雜基胺基、Ν_正辛基胺基雜基胺 =、烧基及芳基磺醯基胺基(較好的是碳數卜%的經取 =或未經取代·基賴基胺基、碳數6〜3q的經取代或 、=代的芳基磧醯基胺基,例如f基麵基胺基、丁基 純基胺基、苯基磺醯基胺基、2,3,5_^苯基磺酿基胺 26 200817477 25795pif.doc 基、對甲基苯基石黃醯基胺基)。當與金屬離子共價結合的取 代基為具有取代基的胺基時,較好的是碳數6〜%的經取 . 代或未經取代的苯胺基、碳數2〜30的經取代或未經取代 ?酿基,基、碳數6〜3G的經取代或未經取代的芳基幾基 ^基、峻數1〜3G的經取代或未經取代的胺絲基胺基、 碳數2〜30的經取代或未經取代的烷氧基羰基胺基、碳數 7〜_30的經取代或未經取代的芳氧基羰基胺基、碳數〇〜3〇 ( 的、纟I取代或未經取代的胺磺醯基胺基、碳數1〜30的經取 代或未經取代的烷基磺醯基胺基、碳數6〜3〇的經取代或 未經取代的芳基4雜胺基;更好的是碳數2〜3()的經取 代,未經取代的醯胺基、碳數6〜3〇的經取代或未經取代 =芳基羰基胺基、碳數丨〜如的經取代或未經取代的胺基 =基胺基、碳數2〜30的經取代或未經取代的烷氧基羰基 ,基、石厌數〇〜3〇的經取代或未經取代的胺石黃酉篮基胺基、 ί〜3〇的經取代或未經取代的烷基磺醯基胺基,更好 $ 的疋蚊數2〜30的經取代或未經取代的醯胺基、碳數2〜 Ζ的經取代或未經取代眺氧基羰基絲、碳數1〜30的 2取代或未經取代的烷基磺醯基胺基,尤其好的是碳數2 、3〇的經取代或未經取代的醯胺基、碳數2〜30的經取代 或未經取代的烷氧基羰基胺基。 當Q為碳環基時,Q較好的是苯基。Q亦可具有除含 冰1金屬離子結合的原子的取代基以外的取代基。就提高 =解}4之觀點而言,較好的是具有取代基。對於此取代基 亚無特別限定,較好的是不為經基、烧氧基、芳氧基、疏 27 200817477 25795pif.doc 基、烷硫基、芳硫基、胺基、烷基胺基及苯胺基中的任一 取代基。作為此取代基,較好的是鹵代基、;6肖基、氧基、 碳數1〜10的經取代或未經取代的烧基、碳數6〜20的經 取代或未經取代的芳基、碳數2〜1〇的經取代或未經取代The substituent which is covalently bonded to the metal ion is preferably a light group or an amine group (preferably an amine group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, and a carbon number of 6 to 30). Substituted or unsubstituted anilino group, such as amine, methylamino, dimethylamino, anilino, N-methylanilino, diphenylamino), acrylamine (preferably A a mercaptoamine group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as an anthranyl group or an acetamidine group. Base, trimethylacetamidoamine, laurylamine, benzhydrylamine, 3,4,5-tri-n-octyloxyphenylamino), aminoaminoamine ( Preferred are substituted or unsubstituted aminopolyamino groups having a carbon number of 1 to 3 Å, such as amine arylamino, N, n-dimethylaminocarbonylamino, N, N- Diethylaminocarbonylamino, morpholinylcarbonylamino), alkoxycarbonylamino (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 3 carbon atoms, for example Methoxycarbonylamino group, ethoxycarbonylamino group , a third butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino group, an aryloxycarbonylamino group (preferably having a carbon number of 7 to 30) Substituted silk-substituted pure amino group, j such as phenoxycarbonylamino, p-phenoxycarbonylamino, m-octyloxyphenoxy-amino), aminesulfonylamino (preferably, carbon number 〇~sun=substituted stimulus __base wire, such as sulfonamide hydrazine, hydrazine, hydrazine _: mercaptoamino group, hydrazine-n-octylamino group Base amine =, alkyl group and arylsulfonylamino group (preferably carbon number % of the obtained = or unsubstituted · lysylamino group, carbon number 6 ~ 3q substituted or = generation Aryl mercaptoamine group, for example, f-based amino group, butyl-purity amino group, phenylsulfonylamino group, 2,3,5-phenylsulfonylamine 26 200817477 25795pif.doc , p-methylphenyl fluorenylamino group. When the substituent covalently bonded to the metal ion is an amine group having a substituent, it is preferably a substituted or unsubstituted aniline having a carbon number of 6 to %. Substituted or unsubstituted aryl group with 2 to 30 carbon atoms a substituted or unsubstituted aryl aryl group having a carbon number of 6 to 3 G, a substituted or unsubstituted aminosilylamino group having a major number of 1 to 3 G, a substituted carbon number of 2 to 30 or Unsubstituted alkoxycarbonylamino group, substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, carbon number 〇~3〇, 纟I substituted or unsubstituted amine sulfonate a mercaptoamine group, a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl-4-heteroamine group having 6 to 3 carbon atoms; Is a substituted or unsubstituted guanamine group having a carbon number of 2 to 3 (), a substituted or unsubstituted = arylcarbonylamino group having a carbon number of 6 to 3 Å, a substituted or unsubstituted carbon number of Substituted amine = arylamino group, substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted amine stone ruthenium basket amine a substituted or unsubstituted alkylsulfonylamino group, preferably a substituted or unsubstituted amidino group having a carbon number of 2 to Ζ Substituted or unsubstituted decyloxycarbonyl a 2-substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, particularly preferably a substituted or unsubstituted decylamino group having 2 to 3 carbon atoms and a carbon number of 2 to 30. A substituted or unsubstituted alkoxycarbonylamino group. When Q is a carbocyclic group, Q is preferably a phenyl group. Q may also have a substituent other than the substituent of the atom to which the ice 1 metal ion is bonded. From the viewpoint of the improvement of the solution = 4, it is preferred to have a substituent. The substituent is not particularly limited, and preferably is not a trans group, an alkoxy group, an aryloxy group, a thiol group, an alkylthio group, an arylthio group, an amine group, an alkylamino group, and Any substituent in the anilino group. As such a substituent, a halogenated group; a 6-octyl group, an oxy group, a substituted or unsubstituted alkyl group having a carbon number of 1 to 10, and a substituted or unsubstituted carbon number of 6 to 20 are preferred. Aryl group, substituted or unsubstituted carbon number 2~1〇
L 的醯基、碳數2〜10的經取代或未經取代的烷氧基羰基、 碳數7〜10的經取代或未經取代的芳氧基羰基、碳數 10的經取代或未經取代的烷基磺醯基、碳數6〜10的經取 代或未經取代的芳基磺醯基、或碳數的經取代或未 經取代的烷氧基磺醯基;更好的是氰基、經取代或未經取 代^碳數1〜10的絲、經取代或未經取代的碳數6〜2〇 的芳基、經取代或未經取代的碳數2〜1〇的醯基、經取代 或未^取代的魏2〜1G的綠基·、經喊或未經取 ^的碳數1〜10的錄獅基、經取代或未娜代的礙數 6〜1〇的絲顧基;更較㈣是經取代或未經取代的石炭 的絲、經取代或未經取代的碳數2〜1G的醯基、 c經取代的碳數2〜1〇 未經取代的碳數1〜1G的垸基顧基。 畐Q為雜環基時,Q在擇 與金^子讀結上或者在Q的取代基上具有 200817477 25795pif.doc 當Q為雜環、且此雜環的取代基上具有與金屬離子典 價結合的原子時,對於此雜環並無特別限定,其例如<舉 出:形成以吡唑(pyraz〇le)環、吡咯(pyrr〇le)環、呋喃 環、嗟吩(thiophene)環、卩米唑環、嗔唑(thiaz〇ie)環、 噁唑(oxazole)環、異噻唑環、異噁唑環、吡啶環、吡嗪 ,、嘧啶(Pyrimidine)環、噠嗪(pyridazine)環、三嗪 ,中的=一環所表示環之基團;較好的是形成以吡唑環、 ^噻唑裱、異噁唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、 ^嘻環任—環所表示環之基® ;更好的是形成以η比唾 衣比°疋娘、二嗪環中的任一環所表示環之基團。 ϋ好岐具轉錄,料其取録並無特別限 疋如可舉出上述r6〜r8中所舉出之取代基。 Q、較好的是峻述Q2形成之含氮雜環。 中,較好的1:=而二;。通式(卜1)與通式(1-2) 的偶氮染料的具體例 "此處,舉出以通式(1 一 1)表 但並不限定於這些具體例。 29 200817477 25795pif.doca mercapto group of L, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, a substituted or unsubstituted carbon number of 10 a substituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, or a substituted or unsubstituted alkoxysulfonyl group having a carbon number; more preferably a cyanogen group; a substituted, unsubstituted or unsubstituted filament having a carbon number of 1 to 10, a substituted or unsubstituted aryl group having a carbon number of 6 to 2 fluorene, a substituted or unsubstituted fluorenyl group having a carbon number of 2 to 1 fluorene , substituted or unsubstituted Wei 2~1G green base ·, shouted or not taken ^ carbon number 1~10 recorded lion base, replaced or not Nadai's obstruction number 6~1〇 silk More; (4) is a substituted or unsubstituted charcoal filament, substituted or unsubstituted carbon number 2~1G fluorenyl group, c substituted carbon number 2~1〇 unsubstituted carbon number 1~1G 垸基顾基. When 畐Q is a heterocyclic group, Q has a substituent on the gold moiety or a substituent on Q has 200817477 25795pif.doc when Q is a heterocyclic ring, and the substituent of the heterocyclic ring has a metal ion value In the case of a bonded atom, the heterocyclic ring is not particularly limited, and for example, it is as follows: a pyrazol ring, a pyrr〇le ring, a furan ring, a thiophene ring, An oxazolidine ring, a thiaz〇ie ring, an oxazole ring, an isothiazole ring, an isoxazole ring, a pyridine ring, a pyrazine, a pyrimidine ring, a pyridazine ring, a group of a ring represented by a ring of a triazine; preferably a pyrazole ring, a thiazole ring, an isoxazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, or a ring. Any group represented by the ring is represented by a ring; it is more preferable to form a group represented by a ring represented by any one of the rings of η than the sputum. The transcription of the cookware is not particularly limited, and the substituents mentioned in the above r6 to r8 may be mentioned. Q, preferably a nitrogen-containing heterocycle formed by Q2. Medium, better 1:= and two; Specific examples of the azo dyes of the formula (1) and the formula (1-2) are exemplified by the formula (1 - 1), but are not limited to these specific examples. 29 200817477 25795pif.doc
(A-l) (A-2)(A-l) (A-2)
(A-3)(A-3)
H3CH3C
(A-9)(A-9)
雖然舉出以通式(1 一2)表示的偶氮染料的具體例, 但並不限定於這些具體例。Although a specific example of the azo dye represented by the general formula (1 - 2) is given, it is not limited to these specific examples.
30 200817477 25795pif.doc (A -10)30 200817477 25795pif.doc (A -10)
•N=N- CN (Α-Π)•N=N- CN (Α-Π)
H3c^n-NHH3c^n-NH
/CN (A -12) ;^丨m广CN n-nh h/CN (A -12) ;^丨mguangCN n-nh h
N - NH (A -15) ,COOEt 、C〇OEtN - NH (A -15) , COOEt , C〇OEt
、S02 N=N- (A -13) a (A-14), S02 N=N- (A -13) a (A-14)
HN — NHN — N
CNCN
H3C VnH H3CH3C VnH H3C
hn~n (A-16)Hn~n (A-16)
VnhVnh
•CH〇 (A-17) ^ /^-N=N ,, Η3〇Ά HN - Ν’•CH〇 (A-17) ^ /^-N=N ,, Η3〇Ά HN - Ν’
H3CH3C
istNh (A -18) •N:istNh (A -18) • N:
H3C—4 ' / N^NH HN N=N*~SvH3C—4 ' / N^NH HN N=N*~Sv
作為上述偶氮金屬錯合物㈣ 叶 或通式⑻表示的贿 合=的是以通式⑷ 觀點而言,更好的^通 、料,就記錄特性之 染料。 表不的偶氮金屬錯合物 =曰就通ί(Α)加以詳細說明。 毛月之偶氮金屬錯合物染料中,.s 為3價時,大多表H / ,在金屬離子的價數⑷中_表=離敝絲構。通式 中的M,較好的或二,子。通式(A) 更較好的是c〇3+。 Fe,更好的是Co3+、Ni3' 原子配縣。所謂配位基,是指與金屬離子結合的 ^二?團。作為配位基,除後述的較佳例中所舉出的 土 X 外’例如可舉出「Photochemistry and Photophyr· — sics 31 200817477 25795pif.doc of Coordination Compounds」(Springer-Verlag 公司, H.Yersm著,1987年發行)、「有機金屬化學_基礎與應用 . (晨華房股份有限公司,山本明夫著,1982年發行)等中 ό己載的配位基。以下,就配位基的具體例加以說明。、 作為上述I;中所含有的、且與Μ配位之原子,較好的 ,,原子、氧原子、硫原子、彻子、鹵素原子;更好的 是氮原子、氧原子、鹵素原子;更較好的是氮原子、氧 ^ 子;尤其好的是氮原子。 ( 當L'與Μ配位時,Μ與L·之間所形成的鍵,可為共 價鍵(σ鍵),亦可為配位鍵。即,L,可為陰離子性配位基1 亦可為中性配位基。 1 上述,對於以氮原子與Μ配位的L,並無特別限定,其 可舉出·含氮芳香族雜環配位基{例如吼^定配位基、吼嗪 配位基、嘧啶配位基、噠嗪配位基、三嗪配位基、噻唑酉千己 位基、噁唑配位基、吡略配位基、咪唑配位基、吡唑配位 基、***配位基、噁二唑(〇xadiaz〇le)配位基、噻二唑配 I 位基、以及包含這些配位基的縮合配位基體(例如,ϋ奎琳 (quinoline)配位基、苯幷喔嗤配位基、苯幷味峻配位基 等)、以及這些配位基的互變異構體等}、胺配位基(例如 氨、甲胺、二曱胺、二乙胺、二¥基胺、三乙胺、旅咬 (piperidine)、。底嗪(piperazine)、嗎琳、芳胺等)、苯胺 (aniline)配位基(例如苯胺、N_曱基苯胺、N,N_二甲基 本私:、N,N_一乙基本胺、二苯基胺、基笨胺、N-烧基 石頁醯基苯胺等)、亞胺(imine)配位基、腈(ηϋ)配位 32 200817477 25795pif.doc 土(例如乙腈配位基等)、異腈配位基(例如第三丁基显腊 . ㈣立基等)、醯胺配位基(例如二甲基甲醯胺配位基、^ . 基乙3議配位基等)。這些配位基亦可具有取代基。 ,對於以氧原子與M進行配位之L,並無特別限定,其可 舉出··醇配位基(較好的是碳數為1〜30,更好的是碳數 為L〜20,尤其好的是碳數為1〜10,例如可舉出使甲醇、 乙醇丁醇、2-乙基己氧基(2_ethylheXyl〇Xy )等中的質子 解#而成之1價陰離子配位基)、芳氧基配位 (2為6〜3〇’更好的是碳數為6〜2(),尤其好的是碳= ,例如可舉出使苯酚、卜萘酚(naphth〇1)、芡酚 中的質子解離而成之Hf陰離子配位基)、二酮((Ης·) 配位基(例如乙醯丙酮(acetylacetone)配位基)、石夕烧氧 基配位基(較好的是碳數為3〜40,更好的是碳數為3〜 3〇,士其好的是碳數為3〜24,例如可舉出三甲基石夕烧氧 基、二苯基石夕烧氧基等)、_己位基(包含環狀驗)、叛酸 配位基、賴配位基、H2q配位基(啊吻⑷、〇2配位 I; 基等。這些配位基亦可具有取代基。 對於以硫原子與]V[進行配位之L,並無特別限定,里可 舉出:烧基硫醇配位基(較好的是碳數為卜3〇,更好的 是碳數為1〜20,尤其好的是碳數為1〜12,例如可舉出. 使丁硫醇㈤anethiGl) 子解離而叙—價陰離子 配位基)、芳基硫醇配位基(較好的是碳數為6〜3〇,更好 的是碳數為6〜20,尤其好的是碳數為6〜12,例如硫紛 (thi〇phen〇1)等)、硫醚配位基。這些配位基亦可具有取 33 200817477 25795pii:doc 代基。 T:SP )配位基(較好的是碳數為2 :2的疋碳數為2〜20,尤其好的 =::其?膦、二甲基膦、二乙基膦、二爾)、 S ==1=是碳數為3〜3G,更好的是碳數為4 尤其好的疋碳數為5〜1G,例如可舉 -本基膦K基膦等)。這些配 土 作為與M進行配位之L J J-有取代基。 基、氣配位基、㈣基、伽位自素配位基(氯配位 時,Li::〜十4/圍内的整數,較好的是1或2。η為i J η子性配位基,為1〜3的整數。 是〇或1、Γ〜3耗圍内的整數,較好的是0〜2,更好的 Γ表示1或2,較好的是i。 除以的範圍内,表示通式(A)的負電荷 p表示1〜1〇範圍内的整數,車交好的9 ·) A 是1〜3’更好的是丨或2。 缺的疋1〜4’更好的 陽離Ϊ式二:出χρ:示P價的陽離子。以χρ+表示的 (χ)表示的子[例如可舉出:以下述通式 或2價以上: 以下述通式(xx)表示的2價 (包含¥)子]、或者齡屬離子、驗土金屬離子 34 200817477 25795pif.doc f對k佈溶劑的溶解性之言,# 好的疋以下述通式(x)或通式( 隹子較 通式(χ) Λ〔χχ)表不的銨陽離子。 R41 R44 - fspR42As the above-mentioned azo metal complex (4) leaf or the bribe represented by the formula (8), it is a dye which has a better property in terms of the general formula (4). The azo metal complexes shown in the table = 曰 are explained in detail by ί (Α). In the azo metal complex dye of Maoyue, when .s is trivalent, most of the table H / , in the valence of metal ions (4) _ table = from the silk structure. M in the formula, preferably or two, sub. More preferably, the formula (A) is c〇3+. Fe, better is the Co3+, Ni3' atomic county. The term "ligand" refers to a ^? group bonded to a metal ion. As the ligand, except for the soil X exemplified in the preferred examples described later, for example, "Photochemistry and Photophyr· sics 31 200817477 25795 pif. doc of Coordination Compounds" (Springer-Verlag, H.Yersm) , issued in 1987), "Organic Metal Chemistry _ Basics and Applications. (Chenhua House Co., Ltd., Yamamoto Akio, issued in 1982) and other ligands contained in the sputum. Below, specific examples of the ligand In addition, as the atom contained in the above I; and coordinated to the ruthenium, preferably, an atom, an oxygen atom, a sulfur atom, a chiral, a halogen atom; more preferably, a nitrogen atom or an oxygen atom, a halogen atom; more preferably a nitrogen atom or an oxygen atom; particularly preferably a nitrogen atom. (When L' is coordinated to ruthenium, a bond formed between Μ and L· may be a covalent bond (σ) The bond may be a coordinate bond. That is, L may be an anionic ligand 1 or a neutral ligand. 1 As described above, L having a nitrogen atom coordinated to ruthenium is not particularly limited. The nitrogen-containing aromatic heterocyclic ligand (for example, a hydrazine ligand, a pyridazine) a group, a pyrimidine ligand, a pyridazine ligand, a triazine ligand, a thiazolium hexanyl group, an oxazole ligand, a pyridyl ligand, an imidazole ligand, a pyrazole ligand, a triazole ligand, a oxadiazole (〇xadiaz〇le) ligand, a thiadiazole ligand group I, and a condensed coordination matrix comprising the ligand (for example, a quinoline ligand) , benzoquinone ligand, benzoquinone taste ligand, etc., and tautomers of these ligands, etc.}, amine ligands (eg ammonia, methylamine, diamine, diethylamine) , bis-amine, triethylamine, piperididine, piperazine, phenanthrene, arylamine, etc., aniline ligands (eg aniline, N-mercaptoaniline, N, N_dimethyl basic private:, N, N_ethylethylamine, diphenylamine, phenylamine, N-alkyl fluorenyl aniline, etc.), imine ligand, nitrile (ηϋ) Coordination 32 200817477 25795pif.doc Soil (such as acetonitrile ligand, etc.), isonitrile ligand (such as Ternary butyl wax. (IV), etc.), indole ligand (such as dimethylformamide) Ligand, ^. Further, the ligand may have a substituent. The L which is coordinated to M by an oxygen atom is not particularly limited, and an alcohol ligand may be mentioned. The carbon number is from 1 to 30, more preferably the carbon number is from L to 20, and particularly preferably the carbon number is from 1 to 10, and examples thereof include methanol, ethanol butanol, and 2-ethylhexyloxy group. 2_ethylheXyl〇Xy), etc., proton solution #1's monovalent anion ligand), aryloxy coordination (2 is 6~3〇', and the carbon number is 6~2(), especially good Carbon = , for example, an Hf anionic ligand obtained by dissociating protons in phenol, naphthol (1, and phenol), and a diketone ((Ης·) ligand (for example, acetamidine) Acetone (acetylacetone) ligand, agglomerate oxy ligand (preferably having a carbon number of 3 to 40, more preferably a carbon number of 3 to 3 Å, and preferably a carbon number of 3) ~24, for example, trimethyl sulphate, diphenyl sulphate, etc.), _ hexyl group (including ring test), tickic acid ligand, lysine ligand, H 2 q ligand (Ah kiss (4), 〇 2 coordination I; base, etc. These ligands may also have a substituent. There is no particular limitation on L which is coordinated by a sulfur atom and [V], and a calcined thiol ligand (preferably, the carbon number is 3 Å, and more preferably the carbon number is 1 to 20, particularly preferably a carbon number of 1 to 12, for example, butyl mercaptan (five) anethiGl) dissociated from a valence anion ligand), an aryl mercaptan ligand (preferably The carbon number is 6 to 3 Å, more preferably the carbon number is 6 to 20, particularly preferably the carbon number is 6 to 12, such as sulfur (thi〇phen〇1), etc., and the thioether ligand. These ligands may also have a base of 33 200817477 25795pii:doc. T:SP) ligand (preferably having a carbon number of 2:2 and having a carbon number of 2 to 20, especially good =:: phosphine, dimethylphosphine, diethylphosphine, dier) And S = 1 = is a carbon number of 3 to 3 G, more preferably a carbon number of 4, particularly preferably, the number of carbon atoms is 5 to 1 G, and, for example, a p-phosphinyl K-phosphine or the like can be mentioned. These soils have a substituent as L J J- coordinated to M. Base, gas ligand, (tetra), gamma self-ligand (in the case of chlorine coordination, Li:: ~ 10 4 / integer within the circumference, preferably 1 or 2. η is i J η The ligand is an integer of 1 to 3. It is an integer in the range of 〇 or 1, Γ 〜3, preferably 0 to 2, and more preferably 1 represents 1 or 2, preferably i. Within the range, the negative charge p of the general formula (A) represents an integer in the range of 1 to 1 ,, and the car is good 9 ·) A is 1 to 3', more preferably 丨 or 2. The lack of 疋1~4’ is better. The cation is two: the χρ: the cation showing the P value. The subunit represented by (χ) represented by χρ+ (for example, a divalent (including ¥) subunit represented by the following formula (xx) or an genus ion, Earth metal ion 34 200817477 25795pif.doc f The solubility of the solvent in the k cloth, #好疋 is the following general formula (x) or the general formula (the scorpion is more than the general formula (χ) Λ [χχ) cation. R41 R44 - fspR42
I R43 ( 現就通式(χ )加以說明,r41〜44 原子=基、芳基H4亦可經由連接基團相互鍵ΐ氯 更评細而言,R4!〜R44表示燒基[表示直鍵、支鍵、考 狀的輕取代或未經取代·基。上述絲包含絲(較好 的是,數1〜30的统基,例如甲基、乙基、正丙基、異丙 基、第二丁基、正辛基、二十烷基、2_氯乙基、2_氰基乙 2乙基己基)、j衣;I:元基(較好的是碳數3〜3〇的經取代 或未經取代的環烷基,例如環己基、環戊基、4_正十二烷 基環己基)、雙環烷基(較好的是碳數5〜30的經取代或未 經取代的雙環烷基,即,自碳數5〜30的雙環烷烴中除去 1個氫原子的1價基。例如雙環以,2,2]庚烷-2-基、雙環[2,2,2] 辛烷基),進而亦包含環結構較多之三環結構等。以下 說明的取代基中的烷基(例如烷硫基中的烷基)亦表示此 種概念的烷基]、芳基(較好的是碳數6〜30的經取代或未 經取代的芳基,例如苯基、對甲苯基、萘基、間氯笨基、 鄰十六醯基胺基苯基)。上述基團亦町進一步具有取代基。 較好的是,R41〜R44中的至少〆個是碳數為1〜10的 35 200817477 25795pif.doc 10的經取代或未經取 經取代或未經取代的烷基、碳數卜 代的芳基。 通式(XX )I R43 (now described by the formula (χ), r41~44 atom=base, aryl H4 may also be bonded to each other via a linking group, and R4! to R44 represent a burning group [indicating a direct bond] , a bond, a lightly substituted or unsubstituted group of the test. The silk contains silk (preferably, a number of 1 to 30, such as methyl, ethyl, n-propyl, isopropyl, Dibutyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl 2-ethylhexyl), j coat; I: a carboxyl group (preferably a carbon number of 3 to 3 Å) a substituted or unsubstituted cycloalkyl group such as a cyclohexyl group, a cyclopentyl group, a 4-n-dodecylcyclohexyl group, a bicycloalkyl group (preferably a substituted or unsubstituted carbon number of 5 to 30) a bicycloalkyl group, that is, a monovalent group from which one hydrogen atom is removed from a bicycloalkane having 5 to 30 carbon atoms, for example, a bicyclic ring, 2,2]heptan-2-yl, bicyclo[2,2,2] octyl The alkyl group further includes a tricyclic structure having a large ring structure, etc. The alkyl group in the substituent described below (for example, an alkyl group in an alkylthio group) also represents an alkyl group or an aryl group of this concept (more) Good is substituted or unsubstituted carbon number 6~30 An aryl group, for example, a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, an o-hexadecanylaminophenyl group. The above group further has a substituent. Preferably, it is in R41 to R44. At least one of the substituted or unsubstituted alkyl or carbon numbered aryl groups of the carbon number of 1 to 10, which is substituted or unsubstituted.
現就通式(X X )加以說明。R45〜R各自獨立表示 氫原子、烷基、芳基。nil表示2〜的整數。有多數個 存在的R45〜R47,可相同亦可不同。L表示炫基連接基團 (内部亦可含有-0-或-S-)或芳基連接基團(内部亦可含 有或-S-)。R45〜R47亦可經由連接基團相互鍵結。r45 〜R47以及L,亦可進一步具有取代基。 較好的是,R45〜R47中的至少一個為碳數1〜10的經 取代或未經取代的烷基、碳數6〜10的經取代或未經取代 的芳基。 i nil較好的是2〜8的整數,更好的是2〜4的整數, 更好的是2或3,尤其好的是2。 L較好的是碳數1〜10的經取代或未經取代的烷基連 接基’更好的是碳數1〜5的經取代或未經取代的烧基連接 f,更好的是碳數1〜3的經取代或未經取代的烷基連接 基。 具體,料有機陽離子的具體例,但並*蚊於這些 36 200817477 25795pif.doc (X-l) (X 〜2) (X-3) Θ' α (Χ-4) 丨八八丨The general formula (X X ) will now be described. R45 to R each independently represent a hydrogen atom, an alkyl group or an aryl group. Nil represents an integer of 2 to. There are a large number of existing R45~R47, which can be the same or different. L represents a thiol linking group (which may also contain -0- or -S-) or an aryl linking group (which may also contain or -S-). R45 to R47 may also be bonded to each other via a linking group. R45 to R47 and L may further have a substituent. It is preferred that at least one of R45 to R47 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. I nil is preferably an integer of 2 to 8, more preferably an integer of 2 to 4, more preferably 2 or 3, and particularly preferably 2. L is preferably a substituted or unsubstituted alkyl linking group having a carbon number of 1 to 10, more preferably a substituted or unsubstituted alkyl group having a carbon number of 1 to 5, more preferably carbon. Number 1 to 3 of substituted or unsubstituted alkyl linking groups. Specifically, specific examples of organic cations, but also * mosquitoes in these 36 200817477 25795pif.doc (X-l) (X ~ 2) (X-3) Θ ' α (Χ-4) 丨 八丨
(X - 5) α (Χ〜6) (Χ-7) β/一·'\ Η2Ν , (Χ-8) Θ'(X - 5) α (Χ~6) (Χ-7) β/一·'\ Η2Ν , (Χ-8) Θ'
(Χ-10)(Χ-10)
(X -14)(X -14)
(Χ-12) Η〇^ ΗΟ-ΝΗ^〇η (Χ-15) η2νφ(Χ-12) Η〇^ ΗΟ-ΝΗ^〇η (Χ-15) η2νφ
(X -16) (Χ-17)(X -16) (Χ-17)
H3C- Η?Ν、 (Χ~18) Φ H3|sjH3C- Η?Ν, (Χ~18) Φ H3|sj
(X -19) η2νθ(X -19) η2νθ
(X - 20)(X - 20)
φ μη·、 (Χ-21)α (Χ-23)Φ μη·, (Χ-21)α (Χ-23)
(X- 24) Ο α Η〆· (X - 25) (Χ-22) \θ(X- 24) Ο α Η〆· (X - 25) (Χ-22) \θ
L2•表 中以*表示與通式(Μ)或料(1-2) ^離子_基上的氫原子同時解離而獲得之The L2• table is represented by * at the same time as the hydrogen atom on the formula (Μ) or the material (1-2) ^ ion _ group is simultaneously dissociated.
2價偶 以通式,式(Α)表不的偶氮金屬錯合物染料,較好的是 "2〜丨)或通式(3〜1)表示的偶氮金屬錯合物染 37 200817477 25795pif.doc 料 現就上述通式(2 通式(2—:〇中#八p )加以况明河表不金屬離子, 料W U中的金屬離子 叶 圍亦相同。 丁。上述i屬料_,較佳範 L1與上述L’同羲。 Q2表示形成錢雜環的原子群4 q2 環基,較好的是以部分結 成::_The azo metal complex dye represented by the formula (式) is preferably a divalent metal complex dye represented by the formula (Α) or the azo metal complex represented by the formula (3 to 1). 200817477 25795pif.doc It is said that the above formula (2 formula (2—: 〇中#八p) is not metal ions in the Mingming River, and the metal ion leaf circumference in the material WU is also the same. D. The above i genus _ Preferably, the preferred formula L1 is the same as the above L'. Q2 represents an atomic group 4 q2 ring group forming a heterocyclic ring, preferably formed in part::_
(q-1 卜υ。 )(q〜2)表不的壤,更較好的是 (q~4)(q-1 Divination.) (q~2) The soil that is not shown, more preferably (q~4)
N一 N k 5^r1〇4 N K H (q-D r! r2N - N k 5^r1〇4 N K H (q-D r! r2
…N N H (q 一 2) (q - 3) _/R101 Rl〇3 N、...N N H (q a 2) (q - 3) _/R101 Rl〇3 N,
、R102 j ,N H 上述部分結構式(q—n〜,—4、由 =n-美的紗m J )9 q—4)中’表示與〜n N基的鍵結位置,R1、r2、r1〇1〜r1〇4各自獨立 原子或者取代基。 ’、風 m就提高溶解性之觀點而言,較好的是R1、R2、Rm〜 R為取代基。作為取代基,可舉上述r6 8 取代基。 衣不的 一 Rl ’較好的是選自碳數6〜20的經取代或未經取代的 芳基、妷數2〜1〇的經取代或未經取代的烷氧基羰基、碳 數7〜10的經取代或未經取代的芳氧基羰基、碳數2〜忉 的經取代或未經取代的烷基胺基羰基、碳數7〜10的經取 代或未經取代的芳胺基羰基、碳數1〜1〇的經取代或未經 取代的烧基確基、碳數6〜10的經取代或未經取代的芳 200817477 25795pif.doc 基石頁醯基、氰签τ〜丞图,又好的是選自碳數6〜2〇的經 取代或未經取代的芳基、碳數2〜1〇的經取代或未經取代 ^完氧基减、魏7〜1㈣經取代或未經取代的芳氧基 ,基、碳數1〜1G _取代或未經取代的絲顧基、礙 10的經減或未經取代料基麵基、氰基中之基 好的是選自碳數2〜1G的經取代或未經取代的烧 =广10的經取代或未經取代的芳細 6〜1〇1 取代或未經取代的燒基磺醯基、碳數 〇的經取代或未經取代的芳基 團,尤其好的是氰基。 i祕中之基 R2,較好的是氫原子、碳數 代的烧基、碳數6叫。的經取代或未二未經取 解性之觀點而士 . P此ΑΑ β⑴紅未、,工取代的方基;就溶 ^ 6^10 燒基,較好的是魏3〜6 芳基。作為 〜6的第三烷基。 儿基,更較好的是碳數4 R 、R1Q2的具體例以及較佳例玺&κ 樣,R103、rH)4& j等的砰細内容與Ri同 的具體例及較佳例等 通式(2—υ中^6!^ 谷與R同樣。 以及r7同義,’二 與通式(卜1)中的R6, R102 j , NH The above partial structural formula (q-n~, -4, by the yarn of the n-mei yarn m J ) 9 q-4) indicates the bonding position with the n n N group, R1, r2, r1 〇1~r1〇4 are each an independent atom or a substituent. From the viewpoint of improving the solubility of the wind m, it is preferred that R1, R2 and Rm to R are substituents. The substituent is the above-mentioned r6 8 substituent. Preferably, R1 is not a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having a number of 2 to 1 fluorene, and a carbon number of 7 a substituted or unsubstituted aryloxycarbonyl group of ~10, a substituted or unsubstituted alkylaminocarbonyl group having a carbon number of 2 to fluorene, a substituted or unsubstituted arylamino group having a carbon number of 7 to 10. a carbonyl group, a substituted or unsubstituted alkyl group having a carbon number of 1 to 1 fluorene, a substituted or unsubstituted aryl group having a carbon number of 6 to 10, 200817477, 25795 pif.doc, a sulfhydryl group, and a cyanide group Further, it is preferably a substituted or unsubstituted aryl group having a carbon number of 6 to 2 fluorene, a substituted or unsubstituted oxy group having a carbon number of 2 to 1 fluorene, or a substituted 7 to 1 (four) or Unsubstituted aryloxy group, group, carbon number 1~1G _ substituted or unsubstituted thiol group, hindered or unsubstituted base group of hindered 10, good base in cyano group is selected from Substituted or unsubstituted calorific acid = 2 G substituted or unsubstituted aromatic fine 6~1〇1 substituted or unsubstituted sulfonylsulfonyl group, substituted with carbon number 〇 Or unsubstituted An aryl group is particularly preferably a cyano group. The base of i secret is R2, preferably a hydrogen atom, a carbon-based burnt group, and a carbon number of six. The viewpoint of substitution or non-incompatibility is P. ΑΑ β(1) red, and the substituted group; in the case of a 6^10 alkyl group, it is preferably a wei 3~6 aryl group. As a third alkyl group of ~6. More preferably, the specific examples of the carbon number 4 R and R1Q2, and the specific examples of the 碳 & κ-like, R103, rH) 4 & j, etc., and the specific examples and preferred examples of the same The general formula (2—υ^^^^ valley is the same as R. and r7 is synonymous, 'two and R6 in the general formula (Bu 1)
我,#乂佳範圍亦相同。 T W K q表示1〜4,較好的是1或2。 111表示1或2’nl較好的是2。 表示0〜3的整婁丈,較好 1 ° 疋〇2’更好的是0或 39 200817477 25795pif.doc n3是在0<n3$4的範圍内,表示以q/p算出之值。 p表示1〜10範圍内的整數’較好的是1〜4,更好的 是1〜3,更好的是1或2。 以下,舉出以通式(2 — 1)表示的偶氮金屬錯合物染 料的具體例,但並不限定於這些具體例。I, #乂佳范围 is also the same. T W K q represents 1 to 4, preferably 1 or 2. 111 indicates that 1 or 2'nl is preferably 2. It means that the whole length of 0~3 is better, 1 ° 疋〇 2' is better 0 or 39 200817477 25795pif.doc n3 is in the range of 0 < n3$4, indicating the value calculated by q/p. p represents an integer in the range of 1 to 10, preferably 1 to 4, more preferably 1 to 3, still more preferably 1 or 2. Hereinafter, specific examples of the azo metal complex dye represented by the formula (2-1) are given, but are not limited to these specific examples.
(M-4) (Μ — 5) (M—6) 、OCH3 hN\、,、 3〇 X',/ Co, ch3 (M — 7)(M-4) (Μ - 5) (M-6), OCH3 hN\,,, 3〇 X', / Co, ch3 (M — 7)
H3CO H3C02SHNV^T NvH3CO H3C02SHNV^T Nv
n-n H3COV^N^och3 f0〆 NC、 nhso2ch3/ trN-n H3COV^N^och3 f0〆 NC, nhso2ch3/tr
(M-8) EtOOC yN H3C(M-8) EtOOC yN H3C
H3CH3C
yV'、/㈣ ' / /tVH3yV', / (four) ' / /tVH3
(M — 9) a(M — 9) a
.N>r^N.N>r^N
,ch3 0|H〆 鍵社=(2—D描繪有偶氮配位基上的陰離子位於㈣ 為二、原子上’但陰離子並不限於存在、、 士在偶氮配位基的整體骨架上 原、子上,可 成為互變異構結構。此情 。。匕的狀態,亦可 *於从下說明的通式(3—η 40 200817477 25795pif.doc, ch3 0|H〆 bond company = (2-D depicts that the anion on the azo ligand is located at (4) is two, on the atom 'but the anion is not limited to existence, and the original skeleton of the azo ligand is , sub-, can become a tautomeric structure. This situation. The state of 匕, can also be * from the following formula (3 - η 40 200817477 25795pif.doc
M,就々述通式(3-1)加以說明。通式(3〜n由 M、Q、R6、τ 1 ^ + q I、v 3 1)中的 範圍亦相同。通犬Γ3 '〜二:、p以及q同義’較佳 的圮同義,較佳範圍亦相同。 )中 、,以下,舉出以通式(3-1)表示的偶氮金屬錯合物染 料的具體例,但並不限定於這些具體例。 41 200817477 25795pif.docM, the description of the general formula (3-1) will be described. The range of the general formula (3 to n from M, Q, R6, τ 1 ^ + q I, v 3 1) is also the same. Tongsong 3 '~2:, p and q synonymous' are better synonymous, and the preferred range is also the same. In the following, specific examples of the azo metal complex dye represented by the formula (3-1) are given below, but are not limited to these specific examples. 41 200817477 25795pif.doc
(M-26) (M-27)(M-26) (M-27)
(M — 28)(M — 28)
(M-31)(M-31)
Θ NH4 本發明之偶氮金屬錯合物染料中,當金屬離子的價數 為2價時,大多表示以通式(B)所表示的配位結構。 現就通式(B)加以說明。通式(B)中的L2·與通式 (A)中的L2_同義,較佳範圍亦相同。其中,ΙΛ中的Q,Θ NH4 In the azo metal complex dye of the present invention, when the valence of the metal ion is two, most of them represent a coordination structure represented by the formula (B). The general formula (B) will now be described. L2· in the general formula (B) has the same meaning as L2_ in the general formula (A), and the preferred range is also the same. Among them, Q in the middle,
尤其好的是σ比嗤環。 L2為中性配位基,可舉出通式(Α)中的Lf中所說明 的中性配位基。 Μ表示2價的金屬離子(包含金屬氧化物離子),較 好的是Cu2+、Ζη2+,更好的是Cu2+。 s表示1〜4範圍内的整數,較好的是4。 t表示0〜14範圍内的整數,較好的是0〜6的整數, 更好的是0〜4的整數。 42 200817477 25795pif.doc 是5 y 為大於等於S的整數1較好的Especially good is the σ ratio ring. L2 is a neutral ligand, and a neutral ligand described in Lf in the formula (Α) can be mentioned. Μ represents a divalent metal ion (including a metal oxide ion), preferably Cu2+, Ζη2+, more preferably Cu2+. s represents an integer in the range of 1 to 4, preferably 4. t represents an integer in the range of 0 to 14, preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. 42 200817477 25795pif.doc is 5 y is an integer 1 greater than or equal to S.
γν-為V價的陰離子,可為M 子,兩種離子尹的任-情況均較好Γ 可為有機陰離 社/表*】〜10範圍内的整數,較好的” 正數,更好的是!〜4範圍内的整數=^5範圍内的 内的整數’尤其好的是1或2。 的疋1〜3範圍 對於無機陰離子並無特別限定,Γν- is a V-valent anion, which can be M, and both of the two ions are better than 情况. It can be an integer in the range of ~10, preferably "positive number, better". The integer in the range of ~4 = the integer in the range of ^5' is particularly preferably 1 or 2. The range of 疋1 to 3 is not particularly limited to the inorganic anion.
Ci〇4、PF6·、〇H-、N〇3-、Bf4-、吻;等。牛 t 南素離子、 對於有機陰離子並師難^、 經取代的魏陰離子、經取代或未代或未 經取代或未經取代的亞俩(sul 2咖禮陰離子、 代或未經取代的鱗酸陰離子、經取代或^陰離子、經取 陰離子、經取代或未經取代的魏取代的院氧基 或未經取代的苯氧基陰離子“ 、經取代 ^,,的質子產生解離二二: 、、二取代的絲絲陰離子、經取代 1 f子、經取代或未經取代的幽基陰離:= ==代的顧基胺基陰離子、硫氰酸根(thiGeya_) 陰離子、經取代或未經取代的乙酸丙酉同酸根陰離子等;較 ”取代或未經取代的緩酸陰離子、經取代或未經取 r的尹、酉义陰離子,更好的是經取代或未經取代的緩酸陰離 子。 43 200817477 25795pif.doc w疋在0<w$4的範圍内 衣不通式(B)中的正電 荷除以v之值Ci〇4, PF6·, 〇H-, N〇3-, Bf4-, kiss; Bovine t Nansu ion, for organic anion and difficult to ^, substituted Wei anion, substituted or unsubstituted or unsubstituted or unsubstituted sub-sulphide (sul 2 cauli anion, substituted or unsubstituted scale An acid anion, a substituted or an anion, an anion, a substituted or unsubstituted Wei substituted anoxy group or an unsubstituted phenoxy anion ", substituted by a proton, produces a dissociation two: , a disubstituted filament anion, a substituted 1 f, a substituted or unsubstituted cleavage: = == substituted thiol anion, thiocyanate (thiGeya) anion, substituted or not Substituted propionate acetate anion and the like; more than a substituted or unsubstituted slow acid anion, a substituted or unsubstituted r, an anion, more preferably a substituted or unsubstituted slow acid anion 43 200817477 25795pif.doc w疋In the range of 0°w$4, the positive charge in the underwear (B) is divided by the value of v.
Cl (2C^ai£9^ ° (c) 較嫩或(眺基。Cl (2C^ai£9^ ° (c) is tender or 眺.
或未經取代《料,技岐魏!〜 未 ,烧基’更好的是钱μ的經取代或未 基0 以Q表不的t鱗,較好的是在対環上具有2個取 代基;作為其取代基,可舉出上述R6〜R8f所舉出的取代 基。吡唑環上的取代基中的一個,較好的是選自氰基、烷 氧基羰基、烷基磺醯基中的取代基,更好的是選自氰基、 烷基磺醯基中的取代基,更好的是氰基。吡唑環上二二代 基中的另一個,較好的是碳數1〜10的經取代或未經取代 的烷基、碳數6〜20的經取代或未經取代的芳基,更好的 是碳數1〜6的經取代或未經取代的烷基,更好的是碳數j 〜4的經取代或未經取代的烧基。 作為通式(C),較好的是R6〜R8為竣數ι〜1〇的經 取代或未經取代的烧基、碳數6〜20的經取代或未經取代 的芳基;且吡唑環上的取代基的一個為選自氰基、烧氧基 爹厌基、烧基石黃酸基中的取代基’且σ比σ坐環上的取代基的另 一個為碳數1〜10的經取代或未經取代的烷基、碳數6〜 44 200817477 25795pif.doc 20的經取代或未經取代的芳基;更好的是,R6〜為碳數 1〜6的經取代或未經取代的烧基,且。比哇環上的取代基的 一個為選自氰基、烷基磺醯基中的取代基,且吡唑環上的 取代基另一個為碳數1〜6的經取代或未經取代的烷基,更 好的是R6〜R8為碳數1〜4的經取代或未經取代的烧基, 且吼唑環上的取代基的一個為氰基,且。比唑環上的取代基 的另一個為碳數1〜4的經取代或未經取代的烧基。 通式(c)中的(yv- ) w 表示(α·)2、(β〇2、( γ)2、(cio4_)2、 (PF6〇2、(bf4_)2、so,、(ch3coo_)2 中之任一者,較好的 是(cr)2、(αο4·)2、S042-、(ch3coc〇2 中之任一者,更好 的是(cr)2、(C104〇2、(CH3CO〇〇2中之任一者,更較好的 是(α·)2、(ch3coct)2 中之任一者。 現舉出以通式(B)表示的偶氮金屬錯合物染料的具 體例,但並不限定於這些具體例。 45 200817477 25795pif.doc 表1 以通式(B)表示的偶氮金屬錯合物染料(s = 4,t==0,u = 5) 化合物例 Μ L2- (YV—) W (Μ—13) Cu2+ yL e^N H3C (CH3CO〇)2 (Μ-14) Cu2+ ^νθ e N φ H3CO2SHN (Cl〇4~) 2 (M-15) Cu2+ yl e-N h3c S042_ (M-16) Cu2+ γΐβ e" h3c (CD 2 (M-17) Cu2+ Νμβ eN^ h3c (PF4") 2 (M-18) Cu2+ κίΝ=Ν-^ν^ yl e^N h3c eo3s人入人of (M-19) Cu2+ .osO ^n=nVv^ ν”θ ^ N h3c (CH3COO一)2 46 200817477 25795pif.doc 表2 以通式(B)表示的偶氮金屬錯合物染料(s=4,t=0,u=5) 化合物例 Μ L2- (Yv—) w (M-20) Cu2+ p Γ EtOOC I yNe e" h3c (CH3CO〇)2 (Μ—21) Cu2+ N|^Ne N h3c (CH3COO-) 2 (Μ—22) Cu2+ γΐβ eN^N h3c S〇42- (Μ-2 3) Cu2+ y,e 〇N^N h3c (CIO,)2 (Μ—24) Cu2+ rv〇CH3 ^^-N=N— y^B ㊀ a nhso2ch3 (CH3COO~) 2 (Μ-2 5) Cu2+ N〇N0 © Φ HNV H Cl (CH3COO—) 2 (Μ—32) Cu2+ v IiliN=NVv^ Ηίβ eN^N (CHsCOO") 2 47 200817477 25795pif.docOr unsubstituted "materials, technology Wei! ~ No, the alkyl group is more preferably a substituted or unbased base of the money μ. The t scale which is represented by Q is preferably two substituents on the anthracene ring; as the substituent, the above may be mentioned. Substituents exemplified for R6 to R8f. One of the substituents on the pyrazole ring is preferably a substituent selected from the group consisting of a cyano group, an alkoxycarbonyl group, and an alkylsulfonyl group, and more preferably a group selected from a cyano group and an alkylsulfonyl group. The substituent is more preferably a cyano group. The other of the di-diyl groups on the pyrazole ring is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Preferred are substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, more preferably substituted or unsubstituted alkyl groups having a carbon number of j 4 . As the general formula (C), R6 to R8 are preferably a substituted or unsubstituted alkyl group having a number of ι1 to 1 Å, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; One of the substituents on the azole ring is a substituent selected from the group consisting of a cyano group, an alkoxy sulfhydryl group, and a pyridyl group, and the other one of the substituents on the σ ratio σ ring is a carbon number of 1 to 10. Substituted or unsubstituted alkyl group, carbon number 6 to 44 200817477 25795pif.doc 20 substituted or unsubstituted aryl group; more preferably, R6~ is substituted or not having a carbon number of 1 to 6 Substituted alkyl, and. One of the substituents on the Biwa ring is a substituent selected from a cyano group, an alkylsulfonyl group, and the other substituent on the pyrazole ring is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. More preferably, R6 to R8 are a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and one of the substituents on the carbazole ring is a cyano group. The other substituent on the azole ring is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. (yv- ) w in the general formula (c) represents (α·)2, (β〇2, (γ)2, (cio4_)2, (PF6〇2, (bf4_)2, so, (ch3coo_) Any of 2 is preferably (cr)2, (αο4·)2, S042-, (ch3coc〇2, more preferably (cr)2, (C104〇2, ( Any one of CH3CO〇〇2 is more preferably any one of (α·)2 and (ch3coct) 2. The azo metal complex dye represented by the general formula (B) is exemplified. Specific examples are not limited to these specific examples. 45 200817477 25795pif.doc Table 1 Azo metal complex dye represented by the general formula (B) (s = 4, t = 0, u = 5) Μ L2- (YV—) W (Μ—13) Cu2+ yL e^N H3C (CH3CO〇)2 (Μ-14) Cu2+ ^νθ e N φ H3CO2SHN (Cl〇4~) 2 (M-15) Cu2+ yl eN h3c S042_ (M-16) Cu2+ γΐβ e" h3c (CD 2 (M-17) Cu2+ Νμβ eN^ h3c (PF4") 2 (M-18) Cu2+ κίΝ=Ν-^ν^ yl e^N h3c eo3s Human-derived (M-19) Cu2+ .osO ^n=nVv^ ν"θ ^ N h3c (CH3COO-) 2 46 200817477 25795pif.doc Table 2 Azo metal complex dye represented by the general formula (B) (s=4, t=0, u=5) Example of compound L2-(Yv-) w (M-20) Cu2+ p Γ EtOOC I yNe e" h3c (CH3CO〇)2 (Μ—21) Cu2+ N|^Ne N h3c (CH3COO-) 2 (Μ—22) Cu2+ γΐβ eN^N h3c S〇42- (Μ-2 3) Cu2+ y,e 〇N^N h3c (CIO,)2 (Μ—24) Cu2+ rv〇CH3 ^^-N=N — y^B a ahhso2ch3 (CH3COO~) 2 (Μ-2 5) Cu2+ N〇N0 © Φ HNV H Cl (CH3COO—) 2 (Μ—32) Cu2+ v IiliN=NVv^ Ηίβ eN^N (CHsCOO" ) 2 47 200817477 25795pif.doc
表3table 3
子亡,但陰離子並不限於=她原 偶氮配位基的整體骨架上廣、、乏’、 可為陰離子在 成為互變異騎構。一那局部化存在的狀態,亦可 另外,對於(M-13)H4g)亦適用,但通式 48 200817477 25795pif.doc (B)中的t可根據化合物所存在的環境而變化。即,在有 上述L’中所舉出的配位基等存在的環境下,***化合物中。 . 通式(B)可根據化合物所存在的環境而變化,但亦 認為其變化是使銅離子的價數發生變化的情況。例如,認 為於溶劑存在下cf變為CU+,認為此時偶氮金屬錯合物 部位成為中性或陰離子性。此時亦假設γν_的數量發生變 化’或者¥>被取代成陽離子(例如通式(Α)中的χρ+等)。 其次,就本實施形態之光資訊記錄媒體的結構加以說 I 明。 —本發明之光資訊記錄媒體的較佳態樣,可舉出下述態 樣(1)及(2)。 態樣(1) ··於厚度0.7 mm〜2 mm的基板上,自基板 侧起依序具有含染料的可錄式記錄層以及厚度_聰〜 〇.5mm的覆蓋層(coverlayer)之光資訊記錄媒體。 態樣(2):於厚度〇·! mm〜1〇 mm的基板上,自基 板側起依序具有含染料的可錄式記錄層以及厚度 ί 〜mm的保護基板之光資訊記錄媒體。 、恶樣(1)中,較好的是在基板上形成的預刻溝槽的執 為50 nm〜500 nm,槽見度為25 nm〜250 nm ,槽深度 為5 nm〜150 nm。態樣(2)中,較好的是在基板上形^ 的預刻溝槽的軌距為200 nm〜500 nm ’槽寬度為5〇 nm〜 3〇〇 rnn,槽深度為30 nm〜丨5〇 _,擺幅(ampiitude ) 為5〜50 nm 〇 [態樣(1)之光資訊記錄媒體] 49 200817477 25795pif.doc 恶樣⑴之光資訊記錄媒體,為至少具有基板 式記錄層以及覆蓋層之態樣。態樣⑴之光資訊 = 的具體例示於圖1。圖1所示的光資訊記錄媒體10A、^ 於基板12上依序具有歧射層18、可錄式記錄層1 =層(ban^ laye〇 2〇、接著層或黏著層22以及覆蓋層 以下,就構成上述結構的材料加以說明。 基板12 (.1 ίΐ )t( Tiltl2 ±Wm'1 ^^^〇ve)34 任一者,下述範圍内的形狀。此上34 ,以達成3己錄$度向於CD —R或DVd__r @ =,此鬚m槽34翻於將本㈣ 2 作對應於藍紫色雷射之媒體的情況。 碑媒粗用 預刻溝槽34的執距是在5G nm〜··的範 限錄好的是小於等於··,更好的 70 mn,更較好的是小於等於33〇㈣。另外,渺= 大二軌距的下限值較好的是大於等於10。nm,更 大=於細,更較好的是大於等於260 nm。若執距 = 則可正確地形成預刻溝槽3心 免串擾(cr〇sstalk) … 可進行高錢記錄。 右軌距小於料· Μ,則 於42的執距’較好的是大於等於1GG nm、小於等 '㈣,更好的是大於等於200_、小於等於370 nm, 50 200817477 25795pif.doc 更較好的是大於等於260nm、小於等於33〇nm。 預„ 34的槽寬度(半值寬:槽深度的ι/2處的槽 二匕^咖〜祝励的範圍内’其上限值較好的是 ,更好,是小於等於23Gnm,更較好的 ,,於等於5。_,更好的是 於大於,100 rnn。若預刻溝槽34的槽寬度大 可抑制記錄成形3村充分地將槽轉印,進而 卞讀錯决率(errorrate)上升;若小於 二二成形時可充分地將槽轉印,進而可避免 5。-::二:寬度半值寬),較好的是大於等於 =nrm,更較好的是大於等於1〜、小於賢 C, 其上在 -,更較=7 _,更好的是小於等於8。 入干乂灯的疋75 nm。另外,預刘、、箠 下限值較好的是大於等於〗。㈣,、二3= 罙度的 ,更較好的是大於箄於— 更好的疋大於專於20 度大於等於5n 、、/ nm。右預刻溝槽34的槽深 degree),若小於箄;^得充分的記錄調變度(nK>dulation 預刻S t ,則可獲得高反射率。 於等=更=罙f,較好喊 m更好的是大於等於20_、小於等於8〇·, 51 200817477 25795pif.doc 更較::是大於等於28nm、小於等於75_。 預刻溝槽34的槽傾斜角度 小於等於80。,更好的是小於等於7Π艮值,較好的是 於,,尤其好的是小於等 更缺的是小於等 槽傾斜角度的下限值,較好的是刻溝f34的 大於等於30。,更較好的是大於等於4t 更好的是 若預刻溝槽34的槽傾斜角 充分的織錯誤(t磁ing 則可獲得 8〇。,則成形性良好。 U振幅,若小於等於 錄式记錄層]4 ,樣(1)之可錄式記錄層14的形成方式是, _ s鮮_溶解於適#的溶射 ^ 2=解於適當的溶劑中,以製備塗佈液,接 、t。於基板上或後述的光反射層上以形成塗膜,然後 進^乾燥、。此處’可錄式記錄層可為單層亦可為疊層,、而 進行多次塗佈塗佈液之步驟則可形成疊層結構。 ,佈液中的染料的濃度,一般是在0.01 wt〇/。〜15 wt% (重罝百分比)的範圍内,較好的是〇1 wt%〜1〇加%的 範圍,更好的是0.5 wt%〜5 wt%的範圍,更較好的是〇 5 wt%〜3 wt°/〇的範圍。 作為製備塗佈液中所使用的溶劑,其例如可舉出:乙 酉夂丁 S曰、乳酸乙酯、乙二醇***乙酸酯(cell〇s〇ive acetate ) 等酯,甲基乙基酮(methyi ethyl ketone )、環己酮 (cyclohexanone)、甲基異丁基酮等酮;二氯甲烷、^孓二 52 200817477 25795pif.doc 氯μ =、氯仿等卣代烴;二甲基甲醯胺等醯胺;甲基環己 烧專k,四虱夫喃、***、二σ惡烧(出〇仰狀)等_ ;乙醇、 正丙!異丙醇、正丁醇二丙酮醇等醇;2,2,3,3-四氟小 ,醇等⑽溶劑;乙二醇單甲_、乙二醇單乙_、丙二醇 單甲_等二醇峻類等。 考慮到所使用染料的溶解性,溶劑可單獨使用或者將 兩種或兩種以上組合使用。進而根據目的不同,而可於塗 布夜中4、力TJ黏合肖彳、抗氧化劑、 滑劑等各種添加劑。 潤 coat)作方法’可舉出:嘴塗法(Spray )、旋塗法(sPin coa! yrt(dlP)'1^^ (blade printin2 Λ刀主佈法U〇Ct〇r Γ〇11〕、網版印刷法(scre^ 、、g)寻。作為塗佈方法,較好的是旋塗法。 圍,曰塗饰液的溫度’較好的是23°c〜50°C的範 圍,更好的是2代〜40〇c的範圍。 ?摩巳 可錄式記錄層14的厚度右、、盖蘇,丨“ , 上為凸部;)上_|,_ an 基板12 是小於等於乃n 季乂好的疋小於等於300 nm,更好的 好的是的是小於等於㈣,尤其 ,更好的是大:下限值’較好的是大於等於1 J疋人於等於3 nm,更征日,A .. 尤其好的是大於等於7_。 、疋大於雜5nm, 另外5可錄式記錄層14的屋 板12上為凹部)上的厚度,較好^凹槽(gr〇〇Ve)40 (基 更好的是小於箄於 好的是小於等於彻膽, 寺於3〇〇_,更較好的是小於等於250麵。 53 200817477 25795pif.doc 其下限值,較好的是大 ,更好的是大;等於川nm,更好的是大於等於 進而,溝執38上的可 上的可錄式記錄層14 、,式忑錄層14的厚度/凹槽40 ,更好的是大^_^厚度之比,較好的是大於等於 尤其好的是大於等於Ο、/3 ’更較好的是大於等於0.15, 更好的是小於等於〇9·,。其上限值,較好的是小於I, 好的是小於等於〇 8。更車乂好的疋小於等於〇·85,尤其 另外,為了進一井挺丄 錄式記錄層14中可可錄式記錄層14的耐光性,可 般使用單態氧抑制二口 f抗褪色劑。作為抗褪色劑,一 中,可藉由將此ttr=oxygenquencher)。本發明 提高。作為單態氧待耐光性進—步 明書::行物中記鶴單態氧抑制劑為爾,專利說 號公報、日本專利特開日刀5出二本專利特開昭1 175693 開昭60-18387號公報、°曰1194士號公報、曰本專利特 報、日本專利特開昭60-19587 昭6〇—19586號公 60--35054號公報、日本專 ^^艮、日本專利特開昭 曰本專利特開昭60 —細昭6〇-36190號公報、 4份4號公報、日本專利日本專利特開昭6〇 — 號公報、曰本專利特 開昭6°,號公報、曰本專利特二 54 200817477 25795pif.doc 報、日本專利特開平4—254 各公報、德國專利料f35Q3 if公報等 言志年1μ號第⑽㈣中記曰本化學會 上述單態氧抑制劑等抗褪色劑的使用早量 11劑九。 0, wt%^5〇 - wt〇/〇〜45 wt%的欽^ 平乂野的疋0·5 <圍,更好的是3 wt%〜40 wt%的範®, 尤其好的是5wt%〜25遍的範圍。 Μ圍’ ΜΜΛΜ ^&_接著層或黏著層22將 π貼合於上述可錄式記錄層14上 阻障層20上。 口丄所不貼合於 定,16,若域明材質的薄膜,則並無特別限 酸樹/取二疋使用聚碳酸醋、聚甲基丙烯酸甲醋等丙烯 气乳乙烯、氯乙烯共聚物等氯化乙稀系樹脂;環 二ί晶系聚稀煙(am〇rph〇usp〇ly〇lefm);聚醋;三 (triaeetyleellulQse)等’其中更好的是使用 石反酉欠目日或三醋酸纖維素。 、#、j外’所謂「透明」,表示對記錄及再生時所使用光的 透過千大於等於80〇/〇。 人另外,後盍層16在不妨礙本發明之效果的範圍内,可 3有各種添加劑。例如,可含有用來截止波長小於等於400 nm的光之Uv吸收劑,及/或用以截止波長大於等於%〇nm 的光之染料。 55 200817477 257y5pif.doc l而作為覆盍層16的表面物性,較好的是,表面扭 =維粗度參數及三維粗度參數中的任-參數均= -ί:=錄及再生時所使用光的聚光度之觀點而 5後盍層16的雙折射較好的是小於等於i〇nm。 、可根據用以進行記錄及再生而被照射之雷射光 黯,NA)來適當規定覆 种,覆蓋層16的厚度,較好的是 在〇.〇1咖〜〇.5 mm的範圍内,更好的是〇 〇5咖 mm的範圍。 · 另外,覆盖層16與接著層或黏著層22加在一起 厚二f好的是_麵〜0.11腿,更好的是_麵 〜U.105 mm。 放層16㈣人射面上亦可設置製造光資訊 祕媒組10A _以防止光人射面產生損傷之保護層(圖 1所不之態樣中為硬化層(hardcoatlayer) 44)。 為了將覆蓋層16與可錄式記錄層14或阻障層2〇加以 貼合,可在兩層之間設置接著層或黏著層22。 接著層中所使用的接著劑,較好的是uv (紫外線) 硬化樹脂、t + | (eleetKm beam,EB)硬彳_旨、埶硬 化樹脂等。 … 當使用uv硬化樹脂作為接著劑時,可將κυν硬化 樹脂直接製備成塗佈液或者將uv硬化樹脂溶解於甲基乙 基酮、乙酸乙酯等適當溶劑中以製備塗佈液,再自分配器 56 200817477 25795pif.doc (dispenser)中供給至阻障2 :製作的光資訊記錄媒體發她曲, ^化娜。此種uv硬化樹脂,例 學工=!限公司製造的The child is dead, but the anion is not limited to = the original skeleton of her original azo ligand is broad, lacking, and the anion can become a mutual variation. A state in which localization exists may also be applied to (M-13)H4g), but t in the formula 48 200817477 25795pif.doc (B) may vary depending on the environment in which the compound exists. In other words, the compound is inserted into the compound in an environment in which the ligand or the like mentioned in the above L' is present. The general formula (B) may vary depending on the environment in which the compound exists, but it is also considered that the change is a change in the valence of the copper ion. For example, it is considered that cf becomes CU+ in the presence of a solvent, and it is considered that the azo metal complex portion becomes neutral or anionic at this time. At this time, it is also assumed that the number of γν_ changes 'or ¥' is substituted with a cation (for example, χρ+ in the general formula (Α), etc.). Next, the structure of the optical information recording medium of the present embodiment will be described. - Preferred aspects of the optical information recording medium of the present invention include the following aspects (1) and (2). Aspect (1) · On a substrate having a thickness of 0.7 mm to 2 mm, a recording layer containing a dye and a cover layer having a thickness of _ _ _ _ 5 mm from the substrate side Record media. Aspect (2): On a substrate having a thickness of 〇·· mm to 1 mm, a photo-recording medium having a recording layer containing a dye and a protective substrate having a thickness of λ mm from the substrate side. In the case of the bad sample (1), it is preferred that the pre-groove formed on the substrate is 50 nm to 500 nm, the groove is 25 nm to 250 nm, and the groove depth is 5 nm to 150 nm. In the aspect (2), it is preferred that the gauge groove of the pre-groove on the substrate is 200 nm to 500 nm 'the groove width is 5 〇 nm to 3 〇〇rnn, and the groove depth is 30 nm 丨5〇_, amplitude (ampiitude) is 5~50 nm 〇 [Speech (1) light information recording medium] 49 200817477 25795pif.doc Weak (1) light information recording medium, which has at least a substrate type recording layer and coverage The aspect of the layer. A specific example of the light information = of the aspect (1) is shown in Fig. 1. The optical information recording medium 10A and the substrate 12 shown in FIG. 1 sequentially have a disparity layer 18 on the substrate 12, a recordable recording layer 1 = layer (ban^laye〇2〇, an adhesive layer or an adhesive layer 22, and a cover layer). The material constituting the above structure will be described. The substrate 12 (.1 ΐ ΐ ) t ( Tiltl 2 ± Wm '1 ^ ^ ^ 〇 ve ) 34 , the shape within the following range. Record the degree of CD-R or DVd__r @ =, and the m-slot 34 is turned over to the case where the (4) 2 corresponds to the medium of the blue-violet laser. The range of 5G nm~·· is recorded to be less than or equal to ·, better 70 mn, and more preferably less than or equal to 33 〇 (4). In addition, the lower limit of 渺 = the second gauge is better. Greater than or equal to 10. nm, larger = finer, more preferably greater than or equal to 260 nm. If the distance = then the pre-groove 3 can be correctly formed to avoid crosstalk (cr〇sstalk) ... can be recorded with high money If the right gauge is smaller than the material · Μ, then the distance of 42 is preferably greater than or equal to 1 GG nm, less than equal '(four), more preferably greater than or equal to 200 _, less than or equal to 370 nm, 50 200817477 25795pi F.doc is more preferably greater than or equal to 260nm, less than or equal to 33〇nm. Pre- 34 slot width (half-value width: slot depth of ι/2 at the slot 2 匕 ^ 咖 ~ 祝 励 范围 ' The upper limit is preferably, more preferably, less than or equal to 23 Gnm, more preferably equal to 5. _, more preferably greater than, 100 rnn. If the groove width of the pre-groove 34 is large, suppression is possible. In the case of recording and forming 3, the groove is sufficiently transferred, and the error rate is increased. If the film is less than two or two, the groove can be sufficiently transferred, thereby avoiding 5. -:: 2: width half width It is preferably greater than or equal to =nrm, more preferably greater than or equal to 1~, less than xian C, which is at -, more than = 7 _, and more preferably less than or equal to 8. 75 nm. In addition, the pre-Liu and 箠 lower limit values are better than or equal to 〖. (4), 2, 3 = 罙, more preferably 箄 — - better 疋 is greater than 20 degrees greater than Equal to 5n, / / nm. The groove depth of the right pre-groove 34), if less than 箄; ^ sufficient recording modulation (nK> dulation pre-etched S t , can obtain high reflectivity. = more = 罙 f, better to say m is better than 20_, less than or equal to 8 〇 ·, 51 200817477 25795pif.doc More:: is greater than or equal to 28nm, less than or equal to 75_. The angle is less than or equal to 80. More preferably, it is less than or equal to 7 Π艮, preferably, especially, less than or equal to less than the lower limit of the equal groove inclination angle, preferably the groove f34 Greater than or equal to 30. More preferably, it is more than or equal to 4t. More preferably, if the groove inclination angle of the pre-groove 34 is sufficient, the t-magnetic ing can obtain 8 turns. The formability is good. U-amplitude, if less than or equal to the record The recording layer of the recording layer 4, the recording layer 14 of the sample (1) is formed by the method of dissolving _ s fresh _ dissolved in the appropriate solution 2 2 solution in a suitable solvent to prepare a coating liquid, And t on the substrate or a light reflecting layer to be described later to form a coating film, and then dried, where the 'recordable recording layer can be a single layer or a laminate, and multiple coating applications The step of the cloth liquid can form a laminated structure. The concentration of the dye in the cloth liquid is generally in the range of 0.01 wt 〇 / 〜 15 wt% (% by weight), preferably 〇 1 wt% 〜 The range of 1% plus % is more preferably in the range of 0.5 wt% to 5 wt%, more preferably in the range of 〇 5 wt% to 3 wt ° / 。. As a solvent used in preparing the coating liquid, Examples thereof include esters such as acetamidine S, ethyl lactate, and cell oxime acetate, and methyl ketone (methyi ethyl ketone) and rings. Ketones such as cyclohexanone and methyl isobutyl ketone; dichloromethane, 孓2 52 200817477 25795pif.doc Chlorine μ = chloroform and other halogenated hydrocarbons; guanamine such as dimethylformamide; methyl ring Already burned k, four scorpion smolder, ether, two sigma smoldering (out of the squat), etc.; ethanol, n-propyl! isopropanol, n-butanol diacetone alcohol, etc.; 2, 2, 3, 3 - tetrafluoroethylene, alcohol, etc. (10) solvent; ethylene glycol monomethyl _, ethylene glycol monoethyl _, propylene glycol monomethyl diol, etc.. Considering the solubility of the dye used, the solvent can be used alone or Two or more types can be used in combination, and depending on the purpose, it can be applied in the night of coating 4, and the force TJ is bonded to various additives such as scorpion, antioxidant, and slip agent. The method of "coating" can be exemplified by: mouth coating method ( Spray ), spin coating method (sPin coa! yrt (dlP) '1 ^ ^ (blade printin2 Λ knife main cloth method U〇Ct〇r Γ〇 11), screen printing method (scre^, g) The coating method is preferably a spin coating method. The temperature of the enamel coating liquid is preferably in the range of 23 ° C to 50 ° C, more preferably in the range of 2 to 40 ° C. Recordable record The thickness of the layer 14 is right, the cover is swelled, and the upper portion is a convex portion; the upper _|, _ an substrate 12 is less than or equal to n, and the 疋 is less than or equal to 300 nm, and more preferably, Less than or equal to (4), especially, better is the greater: lower limit 'better is greater than or equal to 1 J疋 is equal to 3 nm, more levy, A.. especially good is greater than or equal to 7_. 5 nm, the thickness of the other 5 recording layer 14 on the roof panel 12 is a recess, preferably a groove (gr〇〇Ve) 40 (the base is better than a good one is less than or equal to the gallbladder) , the temple is at 3 〇〇 _, and more preferably less than or equal to 250 faces. 53 200817477 25795pif.doc The lower limit value is preferably large, more preferably large; equal to Sichuan nm, more preferably greater than or equal to, and further, the recordable recording layer 14 on the ditch 38, The thickness of the recording layer 14 / the groove 40, more preferably the ratio of the thickness of the large ^ ^ ^, preferably greater than or equal to, particularly preferably greater than or equal to Ο, / 3 ' more preferably greater than or equal to 0.15, More preferably, it is less than or equal to 〇9·. The upper limit value is preferably less than 1, and preferably less than or equal to 〇 8. The 疋 85 85 85 85 85 85 85 , , , , , , 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 As an anti-fading agent, one can be made by ttr=oxygenquencher). The present invention is improved. As a single-state oxygen tolerant light into the step-by-step book:: the single-state oxygen inhibitor in the row of cranes, the patent statement, the Japanese patent special open day knife 5 out two patents special open 1 175693 Kai Zhao Publication No. 60-18387, Gazette No. 1194, Special Patent of Sakamoto, Japanese Patent Laid-Open No. 60-19587, No. 60--35054, No. 60--35054, Japanese Specialized, Japanese Patent, Japanese Patent曰 曰 曰 曰 — — — — — — — — — — — — — — — — — 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 Patent application No. 54 200817477 25795pif.doc, Japanese Patent Laid-Open No. 4-254, and German patent material f35Q3 if bulletin, etc., No. 1μ (10) (4), 曰 化学 化学 化学 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述The dosage of the agent is 11 doses of nine. 0, wt%^5〇-wt〇/〇~45 wt% of the ^^ 平乂野疋0·5 < circumference, better is 3 wt% ~ 40 wt% of the Fan®, especially good 5wt% ~ 25 times the range. The ’ ^ amp ^ & _ or the adhesive layer 22 bonds π to the barrier layer 20 on the above-described recordable recording layer 14. The mouth of the mouth is not suitable for the fixed, 16, if the film of the domain material, there is no special acid tree / take two use of polycarbonate, polymethyl methacrylate and other propylene gas, vinyl chloride, vinyl chloride copolymer Ethyl chloride resin; ring ί 系 聚 ( 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 tri tri tri tri tri tri tri tri tri tri tri tri tri tri tri tri tri tri tri tri tri tri tri Cellulose triacetate. "#, j", "transparent" means that the transmission of light used for recording and reproduction is greater than or equal to 80 〇/〇. Further, in addition, the back layer 16 may have various additives within a range that does not impair the effects of the present invention. For example, it may contain a Uv absorber for cutting light having a wavelength of 400 nm or less, and/or a dye for blocking light having a wavelength of 100 大于 nm or more. 55 200817477 257y5pif.doc l As the surface property of the cover layer 16, it is preferable that the surface twist = the dimensional roughness parameter and the three-dimensional thickness parameter are all - parameters: - ί: = used in recording and reproduction From the viewpoint of the condensing degree of light, the birefringence of the ruthenium layer 16 is preferably equal to or smaller than i 〇 nm. The thickness of the cover layer 16 can be appropriately set according to the laser beam to be irradiated for recording and reproduction, NA), preferably in the range of 〇.〇1咖〜〇.5 mm, Better is the range of 〇〇5 coffee mm. In addition, the cover layer 16 is added to the adhesive layer or the adhesive layer 22. The thickness of the cover layer 16 is preferably _ face to 0.11 leg, more preferably _ face to U.105 mm. The layer 16 (4) can also be provided with a light-shielding group 10A _ to prevent the damage of the light-emitting surface (the hardcoat layer 44 in the aspect of FIG. 1). In order to bond the cover layer 16 to the recordable recording layer 14 or the barrier layer 2, an adhesive layer or an adhesive layer 22 may be provided between the two layers. The adhesive used in the next layer is preferably a uv (ultraviolet) hardening resin, a t + | (eleet Km beam, EB) hard enthalpy, a cerium hardening resin or the like. When a uv hardening resin is used as an adhesive, the κυν hardening resin can be directly prepared into a coating liquid or the uv hardening resin can be dissolved in a suitable solvent such as methyl ethyl ketone or ethyl acetate to prepare a coating liquid, and then self-divided. The adapter 56 200817477 25795pif.doc (dispenser) is supplied to the barrier 2: the produced light information recording medium sends her song, ^ Hua Na. Such uv hardening resin, for example, is limited to the company's
阻者層的形成方法並無特別限定,較好的是,於 或可錄式記錄層14的表面(被貼合面)上塗佈 接者劑,於其上載置覆蓋層16,隨後藉由旋塗法 ,接者劑在被貼合面與覆蓋層16之間均勻擴散後使其硬 化0 ,著層的厚度,較好的是(U μιη〜100 μιη的範圍,更 好的是〇·5 μιη〜50 μιη的範圍,更較好的是i μιη〜3〇 的範圍。 作為黏著層中所使用的黏著劑,例如可使用丙烯酸 (acrylic)系、橡膠系、石夕系黏著劑。就透明性、耐久性 =觀點而言,較好的是丙烯酸系黏著劑。作為丙烯酸系黏 ,劑,較好的是使用以丙烯酸2-乙基己酯、丙烯酸正丁酯 等為主成分’且為了提高凝集力而使短鏈的丙烯酸烷基酯 戍甲基丙_酸酉旨例如丙稀酸甲醋、丙烯酸乙醋、曱基丙稀 酸曱i旨,與可成為與交聯劑的交聯點的丙烯酸、曱基丙烯 酉夂、丙稀醢胺(acrylamide)衍生物、順丁稀二酸(maleic acid)、丙烯酸羥基乙酯、丙烯酸縮水甘油酯等進行共聚合 而獲得之黏著劑。可藉由適當調節主成分、短鏈成分與用 以將交聯點加成的成分的混合比率以及這些成分的種類, 200817477 25795pif.doc 二离ί移溫度(丁g)或交聯密度。 或可錄式方法並無特別限定’可在阻障層20 的黏著劑,再於^上η(被貼合面)上均句塗佈特定量 在覆蓋層16的1载置覆盍層16後使其硬化;亦可預先 著劑塗,再r ^、Γ上均勻塗佈特定量的黏箸劑以形成黏 此塗膜貼合於被貼合面上’隨後使其硬化。 售的黏著薄使用預先在覆蓋層16上設置有黏著層之市 好的=== 範圍。 陣的車巳圍’更較好的是ΙΟμιη〜30_的 蓋層另外’亦可利用UV硬化樹脂並藉由旋塗法而形成覆 ί&ί 外,及本發明之效果的範圍内,除了上述必需層以 # :二Ο之光資訊記錄媒體亦可具有其他任意 曰:乍為,、他任意層,例如可舉出··形成於基板^的背面 上t成有可錄式記麟14的-侧為減侧之非形成面 :"有所期差圖像之標記層(label layer)、或者設置 ,基板12與可錄式記錄層M之間之光反射層18(詳細内 谷如^文所述)、設置於可錄式記錄層14與覆蓋層%之間 =阻障層20 (詳細内容如後文所述)、言交置於此光反射層 兵可錄式記錄層14之間之界面層等。此處,可使用紫 夕線硬化樹脂、熱硬化樹脂、以及熱乾燥樹脂等形成上述 200817477 25795pii.doc 標記層 層,可為單層結 另外,上速必需層及任意層中的任一 構亦可為多層結構。 恕才水⑴之光資訊記錄媒體1Qa 射光46的反料料断改_ 為了 的是在基板12與可錚心卵]/丹生Μ的知,較好 W㈣w 式層之間形成光反射層18。 射S 18,例如可藉由將 的光反射⑽質進行46的反射卞间 蒸鑛a_ing),而形二=。(卿_)或離子 r圍、r = 18的層厚,一般是設為10 nm〜300 nm的 犯圍=好的是設為30nm〜2〜範圍。 /上t射率較好的是大於等於70%。 ^射率*的光反射性物質, 丫、The method for forming the resist layer is not particularly limited, and it is preferred to apply a carrier on the surface (adhered surface) of the recordable recording layer 14 and place the cover layer 16 thereon, followed by In the spin coating method, the carrier is uniformly diffused between the bonded surface and the cover layer 16 to be hardened by 0, and the thickness of the layer is preferably (U μιη to 100 μηη, more preferably 〇· The range of 5 μm to 50 μm is more preferably in the range of i μm to 3 3. As the adhesive used in the adhesive layer, for example, an acrylic, a rubber, or a Shichen adhesive can be used. Transparency and durability = an acrylic adhesive is preferred. As the acrylic adhesive, it is preferred to use 2-ethylhexyl acrylate or n-butyl acrylate as a main component. In order to increase the cohesive force, the short-chain alkyl acrylate 戍 methyl propyl acrylate is intended to be, for example, methyl acetoacetate, ethyl acrylate or decyl acrylate, and can be used as a crosslinking agent. Acrylic acid, mercapto propylene oxime, acrylamide derivative, butadiene An adhesive obtained by copolymerizing a maleic acid, a hydroxyethyl acrylate, a glycidyl acrylate, etc., by appropriately adjusting a mixture of a main component, a short-chain component, and a component for adding a crosslinking point. The ratio and the type of these components, 200817477 25795pif.doc ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ Applying a specific amount on the upper surface of the cover layer 16 and then hardening it after placing the cover layer 16 on the cover layer 16; or applying a predetermined amount of adhesive on the r ^ and Γ The tincture is formed to adhere to the surface to be bonded, and then it is hardened. The adhesive thinner used is a good city=== range in which an adhesive layer is provided on the cover layer 16 in advance. It is more preferable that the cover layer of ΙΟμιη~30_ can also be formed by using a UV-curable resin and by spin coating to form a coating, and in addition to the above-mentioned necessary layer, # : 二Ο之光Information recording media can also have any other 曰: 乍,, he For example, the layer is formed on the back surface of the substrate ^, and the side of the recordable recording layer 14 is a non-formed surface on the minus side: "label layer of the image having a difference in appearance Or, the light reflecting layer 18 between the substrate 12 and the recordable recording layer M (detailed as described in the text) is disposed between the recordable recording layer 14 and the cover layer % = barrier layer 20 (Details are described later), interfacial layers placed between the light-reflecting layer recording layer 14 and the like. Here, a violet-line hardening resin, a thermosetting resin, and a heat drying can be used. The resin or the like forms the above-mentioned 200817477 25795 pipi.doc mark layer, and may be a single layer. Alternatively, any of the upper speed necessary layer and any of the layers may have a multilayer structure. The light-reflecting material 18 of the light recording medium 1Qa of the light water (1) is erroneously changed in order to form a light-reflecting layer 18 between the substrate 12 and the scorpion egg, or the W (four) w-type layer. Shooting S 18 can be performed, for example, by reflecting (10) the light to reflect 46 of the inter-dot steaming a_ing). (Qing _) or ion r circumference, r = 18 layer thickness, generally set to 10 nm ~ 300 nm per capita = good is set to 30nm ~ 2 ~ range. / The upper t-shoot rate is preferably 70% or more. ^Light-reflecting substance*, 丫,
Co K J'V'Nb'Ta'^ A卜 C}1、T U、处、Pd、Ir、Pt、CU、Ag、Au、Zn、Cd、 c 屬或者' Sl ' Te ' Pb ' PG、Sn、Bi等金屬及半金 人雨錄/ ^ ° 些光反射性物質’可單獨使用,亦可組 i射性以上使用’或者亦可製成合金使用。這些光 =勿貝中,較好的是Ο,,、。—,』 f好…’尤其好的是AU、Ag、A1或這些金屬的合金, 取好的是Au、Ag或其合金。 (中間層) ㈣之光資訊記錄媒體1GA中,如圖1所示, 、疋可錄式《錄層14與覆蓋層16之間形成阻障層 59 200817477 2^/y^pif.doc 20 〇 為了提阿可錄式記錄層14的保存性、 著™射率、‘傳: 別限疋,例如—般為對氣體或水分的透過性低之松』病 好的是介電體。 低之材料,較 具體而言,較好的是由Zn、Si、Ti、 f Ta等的氮化物、氧化物、碳化物n 成之材料;較好的是施〇2、Ge〇2、Te0、 b物所構Co K J'V'Nb'Ta'^ A Bu C}1, TU, 处, Pd, Ir, Pt, CU, Ag, Au, Zn, Cd, c genus or 'Sl ' Te ' Pb ' PG, Sn Metals such as Bi, and semi-golden rains / ^ ° Some light-reflective substances can be used alone or in combination with 'i-improvement' or alloys. These lights = not in the shell, preferably in the Ο,,,. —,』 f is good...' Particularly good is AU, Ag, A1 or an alloy of these metals, preferably Au, Ag or alloys thereof. (Intermediate layer) (4) In the light information recording medium 1GA, as shown in FIG. 1, the barrier layer is formed between the recording layer 14 and the cover layer 60. 200817477 2^/y^pif.doc 20 〇 In order to improve the preservability of the recording layer 14, the TM rate, and the 'passivity: for example, the permeability to gas or moisture is low, the dielectric is good. The material of the low material is more preferably a material of a nitride, an oxide or a carbide of Zn, Si, Ti, f Ta or the like; preferably, the ruthenium 2, the Ge 〇 2, the Te0 And b
Sn〇2、Zn〇-Ga2〇3、Nb2〇5、Ta2〇5 ;更 、Sn〇2, Zn〇-Ga2〇3, Nb2〇5, Ta2〇5; more,
Zn0-Ga203、Si〇2、Nb2〇5、Ta2〇5。 n〇2、 另外,阻障層20 ’可藉由真空蒸鍍、直流濺射 (賴挪ent sputtering,Dc濺射)、射麵射㈣ 啊版ng,RF _)、離子蒸鐘—咖麵) 寻法而形成。其中,更好的採用滅射法。 更妊Π20的厚度’較好的是一〜遍一的範圍, ,=疋2 nm〜KK) nm的範圍,更好的是3 〜5〇 的範圍。 [態樣(2)之光資訊記錄媒體] 態樣⑵之光資訊記錄媒體至少具有基板、可錄式記 =及保護基板,較好的是貼合型之光資訊記錄媒體。其 代表性的層結構如下所述。 60 200817477 25795pif.doc 層H1層為在基板上順序形成可錄式記錄 f 吉構射層、接者層’且在接著層上設置有保護基板之 層、:反):二可錄式記錄 護基板之結構。 接者層,狀接者層上設置有保 層二3層二 == 上設置有保護基板之結構 保相,^•在此保護層 層錄式記錄 在此光補層上設置有保護基;之^層、光反射層’且 層、層ίίΓ ΐ在基板上順序形成可錄式記錄 置有保護基;之結構反射層,且在此光反射層上設 一邱八口 ⑦ττ更換其中一部分,亦可省略其中 時^可=二錄式記錄層亦可形成於保護基板側,此 兩面進靖、再生之光資訊記錄媒而, 各層可由1層構成,亦可由多麟成。 在美ΐΐ之中’作為態樣(2)之光資訊記錄媒體,以下將 =自基板側依序具有可錄式記錄層、光反射層、接 結基㈣結構作為例子加以詳細說明。具有上述 、一資。fU己錄媒體的具體例示於圖2。示於圖2的光 61 200817477 25795pif.doc 資訊記錄媒體ι〇Β,在其基板24上依序具有可錄式記錄芦 26、光反射層30、接著層32及保護基板28。 '八 基板24 態樣(2)之基板24上形成有預刻溝槽% (引導样 該預刻溝槽具有執距、槽寬度(半值寬)、概度,以^ 幅中之任一者均為下述範圍的形狀。為了達成高 或DVD-R的記錄密度而設置此預刻溝槽% 預刻溝槽36適合於使用光資訊記錄媒體應 藍紫色雷射的髓之情形。 丨為對應於 豆上= 秦Γ6的執距是在200nm〜5〇〇nm的範圍内, 権限值較好的是小於等於45G nm,更好的是小於等於 麵。另外,預刻溝槽%的執距的下限值較好的是大 大於’更好的是大於等於330 nm,更較好的是 發生串擾;若軌距小-= 的I:溝Γ6的槽寬度(半值寬)是在50 _〜300 -小於等靖nm,更較好的是小G_,更好的是 nm。i :」2一,更較好的是大於等於140 時可充寬; 升;若預刿、# 、 可抑制圮錄時的錯誤率上 預刻溝槽36的槽寬度小於等於300 nm’則可魏 62 200817477 25795pii;doc 由於記錄時所形成的訊坑擴大而發生的串擾,進而可 充分的調變度。 預刻溝槽36的槽深度是在30 nm〜15〇 nm的範 内,其上限值較好的是小於等於14〇 _,更好的是小於 於BO _,更較好的是小於等於12〇 。另夕卜,預刻、羞 槽36的槽深度的下限值較好的是大於等於4〇靜更好的 是大於等於50 _,更較好的是大於等於60 nm。若預刻 f,36的槽*度A於等於3G ’則可獲得充分的記錄調 雙度,若預刻溝槽36的槽深度小於等於150 nm,則可莽 得高反射率。 」^ 基板24的厚度—般是在〇.1麵〜1.0mm的範圍内, 較好的是G.2mm〜〇.8 _的範圍,更好的是Q 3 _ mm的範圍。 · 另外,以改善平面性、提高接著力為目的,可在後述 設置有可錄式記錄層26 一側的基板24的表面形成下塗層。 作為下塗層的材料,例如可舉出:聚(甲基丙稀酸甲 丙__甲基丙婦酸共聚物、苯乙稀-順丁稀二酸昕共 邊甲基丙稀_、苯乙稀-乙稀基甲苯 3她、乳石黃化聚乙稀(chlor°sulf°nated polyethylene)、 Γ、聚氯乙稀、氯化聚烯烴、聚酿、聚醯亞胺、 厂欠”-氣乙細共聚物、乙烯_酷酸乙稀酉旨共聚物、聚乙 細、广丙烯、聚碳酸醋等高分子物質;石夕燒偶 couplmg agent)等表面改質劑。 可藉由如下方式形成下塗層:將上述材料溶解或分散 63 200817477 25795pif.doc 於適當的溶劑中以製備塗佈液,隨後藉由旋塗法、浸塗法、 擠壓塗佈法(extrusi〇n c〇at)等塗佈法將此塗佈液塗佈於 基板表面。 I塗層的層厚,一般是在〇.〇〇5 μιη〜2〇 μιη的範圍 内’較好的是〇·〇1 μιη〜1〇 μπι的範圍。 可錄式玄錄層26 悲I (2)之可錄式記錄層%的詳細内容與態樣(^ 之可錄式3己錄層14同樣。. 光反射i 30 ^才本(2)中,為了對雷射光46的反射率 Γ再生雜的功能,可在可戦記錄層2ίί= 〇 30 之先反射層18同樣。 接著層 怨松⑺中’為了提高光反射 28的密著性,亦可在光反鼾届如&曰”俊玟保姜基板 接著層32。 與保護基板28之間設置 中為===層Γ之材料’較好的是光硬化樹脂,发 Τ為了防止碟片的翹曲,較好的3 ,、 料妒lL^ T t的疋硬化收縮率小的光硬化 树月曰。作為此種光固化樹脂,例如 ^化 製造的「SD-640」、「SD〜661 出大本油墨么司 化接著劑)。 」寺口乂硬化樹脂(1^硬 另外,為了使接著層具有彈柯,一 ΛΑ Η , 生接著層32的厚度較好 的疋1 μηι〜1000 μιη的範圍。 于又平乂野 64 200817477 /y^pii.doc 保幾基板 態樣(2)之保護基板28 (假基板(dummy substrate)) 與上述基板12為相同材質,可使用相同形狀的基板。保護 基板28的厚度,一般厚度是〇·1 mm〜1.0 mm的範圍,較 好的是0.2 mm〜〇·8 mm的範圍,更好的是〇.3 mm〜〇 7 mm的範圍。 保護層 態樣(2)之光資訊記錄媒體10B上,根據其層結構, 以對光反射層30或可錄式記錄層26 #進行物理性及化學 性保濩為目的,設置有保護層。 作為保護層所使用材料之例,可舉出·· hS、 =nS Si02、SiO、Si02、MgF2、Sn02、Si3N4 等無機物質; 二可塑性樹脂、M硬化性樹脂、uv硬化性樹脂等有機物 質。 塑/何藉由如下方式形成賴層:經由接著劑將藉由 稱(plastle)的擦出加工喊得的薄賴合於光反射層 i護ί外’亦可猎由真空駿、濺射、塗佈等方法來設置 〜士 13 = ί可^_旨 ' 熱硬化性樹月旨作為保護 猎由將熱可塑性樹脂或熱硬化性樹脂 層。UV魏輯卿絲制時,哪 2 ΓΓ更化性樹脂直接照射uv *,或者將uv硬化』 M W解於輕的溶财以製備㈣液隨後塗佈此 65 200817477 25795pif.doc 並照射uv光使其固化,以Zn0-Ga203, Si〇2, Nb2〇5, Ta2〇5. n 〇 2, in addition, the barrier layer 20 ' can be vacuum evaporation, DC sputtering (Lon ent sputtering, DC sputtering), shot surface (four) ah version ng, RF _), ion steam clock - coffee surface ) Forming the law. Among them, the better use of the killing method. The thickness of the more pregnant 20 is preferably a range of one to one, and a range of = 2 nm to KK), more preferably a range of 3 to 5 Å. [Speech (2) Light Information Recording Medium] The light information recording medium of the aspect (2) has at least a substrate, a recordable record, and a protective substrate, and is preferably a bonded type optical information recording medium. Its representative layer structure is as follows. 60 200817477 25795pif.doc Layer H1 layer is a layer on the substrate that sequentially forms a recordable recording layer, a layer of the carrier layer and a protective substrate on the layer,: reverse): two recordable recording protection The structure of the substrate. The connector layer is provided with a protective layer 2 and 3 layers on the layer of the connector. The structure phase is provided on the protective substrate. The protective layer is recorded on the optical layer. a layer, a light-reflecting layer', and a layer, a layer 层 Γ 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 顺序 ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ Alternatively, the recording layer may be formed on the side of the protective substrate, and the two sides may be formed into a light-receiving information recording medium. Each layer may be composed of one layer or may be formed of multiple layers. In the optical information recording medium of the aspect (2), the following is a detailed description of the structure in which the recordable recording layer, the light reflecting layer, and the joint base (four) are sequentially provided from the substrate side as an example. Have the above, one capital. A specific example of the fU recorded media is shown in FIG. 2. Light 61 shown in Fig. 2 The information recording medium ι has a recordable record 26, a light reflecting layer 30, an adhesive layer 32 and a protective substrate 28 on its substrate 24. The pre-groove % is formed on the substrate 24 of the eight-substrate 24 pattern (2) (the guide sample has a pitch, a groove width (half-value width), an outline, and any one of the widths The shapes are all in the following ranges. This pre-groove % pre-groove 36 is provided for achieving high recording density of DVD-R. The pre-groove 36 is suitable for use in the case where the optical information recording medium should be blue-violet laser. In order to correspond to the onset of the bean = Gentiana 6 is in the range of 200 nm ~ 5 〇〇 nm, the 権 limit is preferably less than or equal to 45 G nm, more preferably less than or equal to the surface. In addition, the pre-groove % The lower limit of the distance is preferably greater than 'better than 330 nm, more preferably crosstalk occurs; if the gauge is small -= I: the groove width (half-value width) of the groove 6 is In the range of 50 _~300 - less than equal um, more preferably small G _, more preferably nm. i : " 2 ii, more preferably greater than or equal to 140 can be widened; #, can suppress the error rate when recording, the groove width of the pre-groove 36 is less than or equal to 300 nm', then Wei 62 200817477 25795pii; doc due to the expansion of the pit formed during recording The crosstalk that occurs can be sufficiently modulated. The groove depth of the pre-groove 36 is in the range of 30 nm to 15 〇 nm, and the upper limit is preferably less than or equal to 14 〇 _, more preferably Less than BO _, more preferably less than or equal to 12 〇. In addition, the lower limit of the groove depth of the pre-engraving and shame 36 is preferably greater than or equal to 4 〇, and more preferably greater than or equal to 50 _, More preferably, it is 60 nm or more. If the groove *degree A of 36 is pre-etched, the groove degree A is equal to 3G', and sufficient recording double degree is obtained. If the groove depth of the pre-grooved groove 36 is less than or equal to 150 nm, High reflectance can be obtained."^ The thickness of the substrate 24 is generally in the range of 〇.1 surface to 1.0 mm, preferably in the range of G.2 mm to 〇.8 _, more preferably Q 3 _ In addition, for the purpose of improving planarity and improving adhesion, an undercoat layer may be formed on the surface of the substrate 24 on the side where the recordable recording layer 26 is provided, which will be described later. For example: poly(methyl propyl methacrylate _ _ methyl propyl fumarate copolymer, styrene - cis butyl succinate yttrium methyl propylene _, styrene - ethylene toluene 3 she, chloro-sulfonated polyethylene, bismuth, polyvinyl chloride, chlorinated polyolefin, poly-broth, poly-imine, factory owed" - gas-ethyl copolymer, ethylene _ cool A surface modifying agent such as a copolymer of ethylene sulphate, a polymer material such as polystyrene, propylene, or polycarbonate; a couplmg agent; etc. The undercoat layer can be formed by dissolving the above materials. Or disperse 63 200817477 25795pif.doc to prepare a coating liquid in a suitable solvent, and then apply the coating liquid by a spin coating method, a dip coating method, an extrusion coating method (extrusi〇nc〇at) or the like. Coated on the surface of the substrate. The layer thickness of the I coating is generally in the range of 〇.〇〇5 μιη~2〇 μιη, which is preferably in the range of 〇·〇1 μιη~1〇 μπι. Recordable Xuan Recording Layer 26 The details of the recordable layer % of the sadness I (2) are the same as those of the recorded form (^ can be recorded in the 3 recorded layer 14). Light reflection i 30 ^才本(2) In order to reproduce the reflectivity of the laser light 46, the same can be applied to the reflective layer 18 of the recording layer 2 ίί = 〇 30. Next, in order to improve the adhesion of the light reflection 28, It can be used in the light reversal period such as & 玟 玟 玟 玟 玟 玟 玟 基板 基板 基板 。 。 与 与 与 与 与 与 与 与 与 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜 姜The warpage of the sheet is preferably 3, and the light hardening tree of the material 妒lL^T t has a small hardening shrinkage rate. As such a photocurable resin, for example, "SD-640" and "SD" manufactured by Chemicals Co., Ltd. ~ 661 Out of the big ink, the smear of the adhesive). ” Temple mouth 乂 hardening resin (1 ^ hard, in addition, in order to make the adhesive layer with a ke, a Η 生, the thickness of the next layer 32 is better 疋 1 μηι ~ 1000 The range of μιη. 于又平乂野64 200817477 /y^pii.doc Protects the substrate substrate (2) of the protective substrate 28 (dummy substrate) and The substrate 12 is made of the same material, and a substrate having the same shape can be used. The thickness of the protective substrate 28 is generally in the range of 〇·1 mm to 1.0 mm, preferably 0.2 mm to 〇·8 mm, and more preferably It is a range of 3.3 mm to 〇7 mm. On the optical information recording medium 10B of the protective layer state (2), physical properties are applied to the light reflecting layer 30 or the recordable recording layer 26 according to the layer structure thereof. For the purpose of chemical protection, a protective layer is provided. Examples of the material used for the protective layer include inorganic materials such as hS, =nS SiO 2 , SiO, SiO 2 , MgF 2 , Sn 02 , and Si 3 N 4 ; An organic substance such as a curable resin or a uv-curable resin. The plastic layer is formed by laminating a thin layer of a light-reflecting layer by means of an adhesive. The outer 'can also be set by vacuum, sputtering, coating, etc. ~ 士 13 = ί can ^ _ _ 'The thermosetting tree is intended to protect the hunting from the thermoplastic resin or thermosetting resin layer. UV When Wei Zheqing silks, which 2 ΓΓ modifying resin directly illuminates uv *, or uv Of "M W dissolved solution to light to prepare a fiscal (iv) then applying this liquid 65 200817477 25795pif.doc uv light is irradiated and cured to
於這些塗佈液巾進—㈣加^層。根據目的’亦可 吸收劑等各種添加劑。 几1^劑、抗氧化劑、UV 保護層的層厚—般是在01卿 其他層 的圍内。 在不損及本發明之效果的範圍内, 樣(2)之光資訊記錄 示上处層以外,態 豆他任音T系版1〇B中亦可具有其他任意層。 ”他=層__容與上述祕 様曰 進而,本菸昍阜朗从 <八他贗Μ樣。 μ么月關於一種將資訊記錄於在基板上呈有 錢層的«訊記錄媒體中之方法 = 貝訊記錄媒體照射雷射光,而將資 含有一種由通式(H)或(1-2)及金屬 、.構成的偶氮金屬錯合物染料的記錄層中。 體的較佳態樣⑴或態樣⑵之光資訊記錄媒 勺貝afU己錄,例如以如下方式進行。These coating liquid wipes are fed into (4) layers. Various additives such as an absorbent may be used depending on the purpose. The thickness of several layers of the antioxidant, UV protective layer is generally within the circumference of the other layers of 01. In the range in which the effect of the present invention is not impaired, the optical information of the sample (2) is recorded in addition to the upper layer, and any other layer may be present in the T-shirt version 1B of the state. "He = layer __ tolerance and the above secrets, and this smog is from the eight scorpion. μ month about a kind of information recorded on the substrate in the rich layer of the information media Method = Beixun recording medium irradiates laser light, and will contain a recording layer of an azo metal complex dye composed of the general formula (H) or (1-2) and a metal. The light information recording medium of the aspect (1) or the aspect (2) has been recorded, for example, in the following manner.
L 、’先 &使光資訊^己錄媒體以固定線速度(例如〇 5 rarl〇m/s)或固定角速度旋轉,一邊自基板侧或保護層 /、射半導體雷射光等記錄用光。藉由照射此光而使雷射 5射部麵光學躲發生變化以記職訊。圖丨所示之 〜t中透過第1物鏡42 (例如數值孔徑NA為〇·85 )自 ,盒層16侧照射半導體雷射光等記錄用雷射光牝。一般 5忍為’藉由照射此雷射光46,使可錄式記錄層14吸收雷 、光46而發生局部性溫度上升,並產生物理或化學變化 (例如生成訊坑)而改變其光學特性,藉此記錄資訊。同 66 200817477 25795pii.doc 樣I於圖2所不之態樣中,透過數值孔徑财例如為0.65 ϋ!;鏡48 ’自基板24側照射半導體雷射光等記錄用 i m=般認為’藉由照射此雷射光46,可錄式記錄 ΐ化㈣化46而發生局部性溫度上升,並產生物理 =子雙化(例如生成訊坑)而改變其光學特性,藉此記 錄貧訊。 “千fi?中’較好的是藉由照射波長小於等於44〇 ™ 資訊。作為記錄光,可較好地使用具有小 ^it Γ範圍的振堡波長之半導體雷射光;作為較 之龄㈣本』千; 一15 nm範圍的振盪波長 ^ 使用光學波導元件使中心振盈波 、',、、nm的紅外半導體雷射光成為二分之一波長的中 ==波長為42、之藍紫色雷射光。特別是在:二 :二:是使用具有390 一15 nm範圍的振盪 1導體雷射m所述經記錄的資訊之再 厗姑:i如下方式進行:一邊以與上述相同的固定線速 半導體、It 板側或保護層侧照射 卞命版田射先,再檢測其反射光。 其-人,就本發明之化合物的合成方法加以說明。 的_= = ^ (l - D及通式O'"2)表示的偶氮染料 報以舉出日本專利特開昭61 —36362號公 但θ、,專利特開2〇06 —57076號公報所記載之方法。 於此,亦可使用其他反應溶劑、酸。另外, 了於如(例如,乙酸鈉、吼唆、氫氧化納等)存在下進 67 200817477 25795pif.doc 行偶合反應。於後述實施例中,利用化合物3)來表 示本發明之一般的偶氮染料的合成方法之例。L, 'First & The optical information is recorded at a fixed linear velocity (for example, ra 5 rarl〇m/s) or a fixed angular velocity, and the recording light is emitted from the substrate side or the protective layer / the semiconductor laser light. By illuminating this light, the laser surface of the laser is changed to record the news. In the case of 〜t, the first objective lens 42 (for example, the numerical aperture NA is 〇·85) is transmitted from the side of the casing layer 16 to the laser beam for recording such as semiconductor laser light. In general, 5 is to 'by illuminating the laser light 46, causing the recordable recording layer 14 to absorb the thunder and light 46 to cause local temperature rise, and to cause physical or chemical changes (such as generating pits) to change its optical characteristics. Use this to record information. In the case of Fig. 2, the numerical aperture is, for example, 0.65 ϋ!; the mirror 48' is irradiated with semiconductor laser light from the side of the substrate 24, and the recording is made by im= The laser light 46 can record the deuteration (four) 46 and cause a local temperature rise, and a physical = sub-double (for example, generating a pit) to change its optical characteristics, thereby recording the poor news. "Thousands of Fi?" is better by irradiating the wavelength of 44 〇 TM information. As the recording light, it is better to use the semiconductor laser light having the vibration wavelength of the small ^ Γ range; as the age (4)千千; an oscillation wavelength in the range of 15 nm ^ using optical waveguide elements to make the central vibration wave, ',,, nm infrared semiconductor laser light into one-half wavelength == wavelength of 42, blue-violet thunder Emitting, especially in: 2: 2: is to use the recorded information of the oscillating 1 conductor laser m with a range of 390 to 15 nm. i: i is performed as follows: one side at the same fixed line speed as above The semiconductor, the It plate side or the protective layer side is irradiated with the test paper first, and then the reflected light is detected. The human, the synthesis method of the compound of the present invention is explained. _= = ^ (l - D and the general formula The azo dye represented by O'"2) is exemplified by the method described in Japanese Laid-Open Patent Publication No. SHO 61-36362, the entire disclosure of which is incorporated herein by reference. Other reaction solvents, acids, and, for example, (for example, sodium acetate, cesium) , Sodium hydroxide, etc.) in the presence of feed line 67 200817477 25795pif.doc coupling reaction. Examples described later on, the use of compound 3) represents a general embodiment of the method of synthesis of azo dyes of the present invention.
作為使偶氮染料與金屬離子反應而獲得偶氮金屬錯人 物染料的一般方法,可舉出:於鹼存在下,於有機溶巧中 或水中或者其混合液中攪拌偶氮染料、金屬鹽(包含,金 屬錯合物、金屬氧化物鹽)之方法。其中,對於金屬_的 種類、驗的種類、有機溶劑或其混合液的種類、反應、应产 等並無限定。現以例示化合物(M— 1)為例來表示 之偶氮金屬錯合物染料的合成方法。 於此合成方法中,藉由於鹼存在下使C〇鹽、Ni趟、 Fe鹽等與以通式(卜丨)或通式(1-2)表示的偶氮染料 反應,而獲得以通式(2-1)或通式(3-υ表示的偶氮 金屬錯合物染料。當反應系統中不存在驗時,通常莽得如 比較化合物(C)或比較化合物(F)的中性偶氮金屬錯人 物、或者具有偶氮㈣(配位基)的氫原子_個都不ςς 的結構的陽離子性偶氮金屬錯合物。藉由於鹼存在 Ζη鹽等與以通式(1_υ或通式(卜2)表示u 木料反應,而獲得以通式(4一 1)或通式(5〜 人 偶氮金屬錯合物染料。#反應祕中不存在驗時 收特辞性、熱分解特性以及耐光性等物性與通式 或通式(5—1)為不同的偶氮金屬錯合物。 以下,利用實施例更具體地說明本發明,但只 出其要點,則本發明並不限定於以下實施例。、 ° 首先,就以通式U-D或(卜2)表示的偶氮染料 68 200817477 25795pif.doc 的合成加以說明,但並不限定於這些方法 的合成] 化合物(2)As a general method for obtaining an azo metal-substituted human dye by reacting an azo dye with a metal ion, an azo dye or a metal salt may be stirred in an organic solvent or in water or a mixture thereof in the presence of a base ( A method comprising a metal complex, a metal oxide salt). Here, the type of the metal, the type of the test, the type of the organic solvent or the mixture thereof, the reaction, the production, and the like are not limited. A method for synthesizing an azo metal complex dye represented by the exemplified compound (M-1) will now be described. In the synthesis method, a C 〇 salt, a Ni 趟, a Fe salt or the like is reacted with an azo dye represented by the formula (dipor) or the formula (1-2) in the presence of a base to obtain a general formula. (2-1) or an azo metal complex dye represented by the formula (3-υ). When there is no test in the reaction system, a neutral couple such as the comparative compound (C) or the comparative compound (F) is usually obtained. a cationic azo metal complex having a structure in which a nitrogen metal is a wrong character or a hydrogen atom having an azo (tetra) (coordination group), which is a structure in which a ruthenium salt or the like is present in the formula (1_υ or Formula (Bu 2) represents u wood reaction, and obtains the general formula (4 - 1) or the general formula (5 ~ human azo metal complex dye. #反应秘秘不存在验时性性性,热分解The azo metal complex which is different from the general formula or the general formula (5-1) in physical properties such as properties and light resistance. Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not intended to It is limited to the following examples. ° First, the combination of azo dyes 68 200817477 25795pif.doc represented by the general formula UD or (b 2) Will be described, but not limited to] Synthesis of Compound these methods (2)
化合物(A—3) MeOH 0 〜5°C N = nCompound (A-3) MeOH 0 〜5°C N = n
[化合物(A — 3[Compound (A-3)
NaN〇2/H2QNaN〇2/H2Q
EtCOzH/AcOH’ 0〜5°CEtCOzH/AcOH' 0~5°C
其次,於加入2 g化合物(1)的10〇如三角燒瓶中 注入2.6 ml乙酸(Ac0H)、4 ml丙酸,=在冰 浴冷卻下緩緩滴加3.7ml鹽酸(35〜37%)。然後,以冰浴 /令πρ至〇C〜5C,並向其中緩緩滴加溶解有ο% g NaN〇2 的j ml水溶液(冷卻至或以下)。隨後,於〇〜 下攪拌15分鐘。將此酸性溶液緩慢加入4〇 持在〜rc的含2.2g化合物⑵之甲醇1^^ 液中,擾拌1小時。接著,恢復至室溫,授拌2小時,隨 後將沈殺物過濾,並以最小量的曱醇清洗。藉由以乙酸乙 酯為溶離液之矽膠管柱層析法(silica gd c〇lumn chr〇matography)將所得固體進行精製,獲得化合物 (Α 〜3)。 ° 藉由300 MHZ】H-NMR來進行化合物的鑑定。ih_nmr (DMS〇-d6) [PPm],· 3·70 (1H,br),13.5 (1H,s),2.46 (3H,s), L51 (9H, s),1·44 (9H,s)。 ’ ’ 藉由與上述化合物(A —3)的合成同樣的方法,合成 (A-7)以及(A一9)。本發明之各種偶氮染料,可同樣 地合成。藉由300 MHzW-NMR來進行化合物的鑑定。以 69 200817477 2^/y^pif.doc 下表示核磁共振(nuclear magneiic res〇nance,Nmr)光譜 資料。 (A- 7 ) : ]H-NMR (DMSO-d6) [ppm] ; 3.95 (2H? br)5 2·47 (3H,s)5 1·52 (9H,s)。 (A-9) : ]H-NMR (DMSO-d6) [ppm]; 3.45 (2H9 br)9 10.06 (1H9 s)? 7.85 (2H, d)5 7.52 (1H9 t)9 7.37 (1H5 d)? 7.24 (1H,t),6,82 (2H,d)5 3·77 (6H,S),3.07 (3H,s),1,44 (9H,s)。 其次’利用.例示化合物就本發明之偶氮金屬錯合物的 合成方法加以說明,但並不限定於這些方法。 [(M—1)的合成;] 化合物(M — 1)Next, 2.6 ml of acetic acid (Ac0H) and 4 ml of propionic acid were poured into a 10 Torr flask such as 2 g of the compound (1), and 3.7 ml of hydrochloric acid (35 to 37%) was gradually added dropwise under ice cooling. Then, an ice bath / πρ to 〇C 5C was added, and a j ml aqueous solution (cooled to or below) in which ο% g NaN〇2 was dissolved was gradually added dropwise thereto. Then, stir under 15 minutes for 15 minutes. This acidic solution was slowly added to a solution of 2.2 g of the compound (2) in a solution of ~rc, and the mixture was stirred for 1 hour. Then, it was returned to room temperature, mixed for 2 hours, and then the precipitate was filtered and washed with a minimum amount of sterol. The obtained solid was purified by silica gel column chromatography (silica gd c〇lumn chr〇matography) to obtain a compound (Α~3). ° Identification of the compound by 300 MHZ] H-NMR. Ih_nmr (DMS〇-d6) [PPm], · 3·70 (1H, br), 13.5 (1H, s), 2.46 (3H, s), L51 (9H, s), 1·44 (9H, s) . (A-7) and (A-9) were synthesized by the same method as the synthesis of the above compound (A-3). The various azo dyes of the present invention can be synthesized in the same manner. Identification of the compounds was carried out by 300 MHz W-NMR. Nuclear magnetic resonance (Nmr) spectroscopy data is presented under 69 200817477 2^/y^pif.doc. (A-7) : ]H-NMR (DMSO-d6) [ppm]; 3.95 (2H? br) 5 2·47 (3H, s) 5 1·52 (9H, s). (A-9) : ]H-NMR (DMSO-d6) [ppm]; 3.45 (2H9 br)9 10.06 (1H9 s)? 7.85 (2H, d)5 7.52 (1H9 t)9 7.37 (1H5 d)? 7.24 (1H,t),6,82 (2H,d)5 3·77 (6H,S), 3.07 (3H,s),1,44 (9H,s). Next, the method for synthesizing the azo metal complex of the present invention will be described using an exemplary compound, but it is not limited to these methods. [(M-1) synthesis;] Compound (M-1)
於50 ml茄形燒瓶中加入3〇〇 mg化合物(A — 3)、20 mi 曱醇,一邊攪拌一邊滴加2·1 ml三乙胺(Et3N)。攪拌1〇 分鐘,進而加入0.7 gCo(OAc)2.4H20,加熱回流(reflux) 1小時。加入50 ml蒸餾水後,恢復至室溫,將沈澱物過 濾。以蒸餾水進行清洗,實施乾燥,獲得〇.9g化合物(μ 一1)。化合物的鑑定是以基質輔助雷射脫附游離質譜法 (Matrix-assisted Laser Desorption/Ionization Mass Spectrometry,MALDI-MS)加以確認。m/z= 762 (nega)、 70 200817477 25795pii.doc 102 (posi) 〇 [化合物(Μ —2)的合成] 依照例示化合物(Μ — 1 )的合成方法,將 Co(OAc)24H20替換成Ni(0Ac)2.4H20,以同樣方式進行反 應,藉此合成化合物(M —2)。化合物的鑑定是以基質輔 助雷射脫附游離質譜法(MALDI-MS )加以確認。m/z = 762 (nega)、102 (posi) 〇 [化合物(Μ — 13)的合成] 化合物(Μ — 1 3) 化合物(A —3) [(Cu24)5(L2')4](Ac〇')23 mg of the compound (A-3) and 20 mmol of sterol were added to a 50 ml eggplant-shaped flask, and 2.1 ml of triethylamine (Et3N) was added dropwise while stirring. After stirring for 1 minute, 0.7 g of Co(OAc) 2.4H20 was further added and refluxed for 1 hour. After adding 50 ml of distilled water, it was returned to room temperature, and the precipitate was filtered. It was washed with distilled water and dried to obtain 9. 9 g of a compound (μ-1). Identification of the compounds was confirmed by Matrix-assisted Laser Desorption/Ionization Mass Spectrometry (MALDI-MS). m/z = 762 (nega), 70 200817477 25795pii.doc 102 (posi) 〇 [Synthesis of Compound (Μ-2)] According to the synthesis method of the exemplified compound (Μ-1), Co(OAc)24H20 was replaced with Ni (0Ac) 2.4H20, the reaction was carried out in the same manner, whereby the compound (M-2) was synthesized. Identification of the compounds was confirmed by matrix-assisted laser desorption mass spectrometry (MALDI-MS). m/z = 762 (nega), 102 (posi) 〇 [synthesis of compound (Μ-13)] Compound (Μ-1 3) Compound (A-3) [(Cu24)5(L2')4](Ac 〇') 2
h3c 依照例示化合物(Μ — 1 )的合成方法,將 Co(OAc)2_4H20替換為Cu(0Ac)2*H20,以同樣方式進行反 應,藉此合成化合物(M — 13)。以ESI-MS (電喷灑游離 質譜法)進行化合物的鑑定。111/^=1724.5、861.7、吸收111^\ =440 nm (丙酮中)。在MALDI-MS中確認有碎片 (fragment)。m/z= 893 (nega)、829 (nega)、415 (posi)、 吸收lmax = 440 nm (丙酮中)。 對化合物(M— 13 )進行電子自旋共振(Electron Spin Resonance,ESR)解析。藉此,於粉末狀態下,確認存在 於Cu2+離子的周圍配位有3個N原子之結構。H3c According to the synthesis method of the exemplified compound (Μ-1), Co(OAc)2_4H20 was replaced with Cu(0Ac)2*H20, and the reaction was carried out in the same manner, thereby synthesizing the compound (M-13). The compounds were identified by ESI-MS (electrospray free mass spectrometry). 111/^=1724.5, 861.7, absorption 111^\=440 nm (in acetone). Fragments were confirmed in MALDI-MS. m/z = 893 (nega), 829 (nega), 415 (posi), absorption lmax = 440 nm (in acetone). The compound (M-13) was analyzed by Electron Spin Resonance (ESR). Thereby, in the powder state, it was confirmed that there was a structure in which three N atoms were coordinated around the Cu2+ ion.
另外,與化合物(M — 13)同樣方式合成化合物(M 71 200817477 25795pif.doc 一21 ),藉由X射線結構解析確認存在以5比4的比例形 成Cu與2價偶氮染料陰離子之結構。 另外,於(M—13 )的合成方法中,藉由於原料中使 用陰離子不同的Cu化合物來代替Cu(0Ac)2.H20,而獲得 (M— 14)、(M— 15)、(M— 16)、(M— 17)等陰離子為不 同的偶氮金屬錯合物。Further, a compound (M 71 200817477 25795 pif. doc-21) was synthesized in the same manner as the compound (M-13), and it was confirmed by X-ray structure analysis that a structure of Cu and a divalent azo dye anion was formed in a ratio of 5:4. Further, in the synthesis method of (M-13), (M-14), (M-15), (M-) are obtained by using Cu compounds of different anions in the raw material instead of Cu(0Ac)2.H20. Anions such as 16) and (M-17) are different azo metal complexes.
可藉由同樣的合成方法,在本發明之範圍内合成各種 偶氮金屬錯合物染料。化合物的鑑定,可藉由 MALDI-MS、ESI-MS、ESR解析、元素分析、X射線結構 解析加以確認。 藉由與化合物(Μ— 1 )同樣的合成方法而獲得之偶氮 金屬錯合物染料,能夠在溶劑中進行陽離子交換反應 下表示陽離子交換反應的合成例。 以 [化合物(Μ—6)的合成1 化合物(Μ — 1) 化合物(3) 化合物(Μ — 6)Various azo metal complex dyes can be synthesized within the scope of the present invention by the same synthesis method. The identification of the compound can be confirmed by MALDI-MS, ESI-MS, ESR analysis, elemental analysis, and X-ray structure analysis. The azo metal complex dye obtained by the same synthesis method as the compound (Μ-1) can be synthesized by a cation exchange reaction under a cation exchange reaction in a solvent. [Compound of compound (Μ-6) 1 compound (Μ-1) compound (3) compound (Μ-6)
於50 ml茄形燒瓶中加入300 mg化合物(M-1)、1〇 ml曱醇:一邊授拌—邊添加將200 mg化合物(3)溶解於 5 ml f醇與5 ml蒸鶴水中而獲得的溶液,加熱回流1小 72 200817477 25795pif.doc 時。加入20 ml蒸餾水後,恢復至室溫,將沈澱物過濾。 • 以蒸餾水清洗,實施乾燥,而獲得270 mg化合物(M —^)。 . 化合物的鑑定是以MALDI_MS法加以確認。m/z二 762(nega)、297(p0si)。 可藉由與上述化合物(M—6)的合成方法同樣的方 法,合成本發明之各種含有陽離子的偶氮金屬錯合物染料。 依照化合物(M—6)的合成方法進行陰離子交換,亦 (;:可獲得如(M—18)的含有有機陰離子的偶氮金屬錯合物。 [比較化合物(c)的合成] 比較化合物(C):日本專利特開2006 — 142789號公 報範脅的化合物 於50 ml茄形燒瓶中加入100mg化合物(a —3)、3 ml 曱醇,一邊攪拌一邊加入34mgNiCl2.6H20,攪拌30分鐘。 力^入20 ml蒸顧水後,將生成的沈殿物過濾。以蒸館水清 洗,貫施乾燥,獲得Π0 mg比較化合物(C)。化合物的 ( 鍰定是以MALDI-MS法加以確認。m/z=763.5 (p0si)。 v [光資訊記錄媒體的製作] (基板12的製作) I作厚度為1.1 mm、外徑為120 mm、内經為15 rnm 且具有螺旋狀預刻漠槽34 (執距320 nm、槽寬度··凹_ 4〇 (凹部)寬度190 nm、槽深度:47 nm、槽傾斜角度: 65、擺幅:20 nm)的、由聚碳酸酯樹脂構成的射出成形 基板。射出成形時所使用的母版(stamper)的母帶處理 (mastering),是利用雷射切割(iaser cutting) (351 nm) 73 200817477 25795pif.doc 而進行。 (光反射層18的形成) 使用Unaxis公司製造的Cube,於&氣環境中,藉由 DC滅射在基板12上形成膜厚6〇nm的作為直空成膜声 ANC 光反射層(Ag :⑽ at%、Nd : 〇 7 娜、& : 〇 9 ^ )。 藉由濺射時間來調整光反射層18的膜厚。 (可錄式記錄層14的形成) 實施例1〜10 :將化合物 16)、(M-17)、(M-22)、(M-23)、(m—26)、(m—%)、 (]\^—2)、(]\4一38)各18添加溶解於1〇〇11112,2,3,3_四氟 丙醇中,製備含有染料的塗佈液。接著,藉由旋塗法,一 邊使旋轉數自500 rpm至2200 rpm内變化,一邊於23°C、 50%RH的條件下,於光反射層18上塗佈經製備的含有染 料的塗佈液,以形成可錄式記錄層14。 形成可錄式記錄層14後,以潔淨烤箱(dean oven) 實施退火(anneal)處理。退火處理,是在垂直的堆疊柱 上以分隔片形成間隔同時將基板12加以支持,於8〇cc下 保持1小時。 (阻障層2〇的形成) 隨後’使用Unaxis公司製造的Cube,於Ar氣環境中, 藉由DC濺射於可錄式記錄層14上形成由Nb2〇5構成的厚 度為10 nm的阻障層20。 (覆蓋層16的貼合) 覆盍層16,是使用内徑為15 mm、外徑為120 mm且 74 200817477 257y5pif.doc 在一面上具有黏著層(玻璃轉移溫度_26t)的聚碳酸酯製 薄膜(TeijinPUREACE,厚度:80μιη),並以此黏著層= 聚碳酸酯製薄膜的合計厚度成為100 μπι的方式加以設9定 接著,於阻障層20上,以此阻障層20與黏著層相抵 接之方式載置覆蓋層’隨後擠壓此覆蓋層使其壓接並貼 合於構件上。藉由以上步驟,製作具有圖丨所示的層結構 之光資訊記錄媒體10Α。 藉此’製作實施例1〜10之光資訊記錄媒體。 (比較例1〜8)光資訊記錄媒體的製作 除使用比較化合物(Α)〜(Η)代替例示化合物(Μ —1)作為可錄式記錄層14中所使用的染料以外,其餘以 同樣的方法製作比較例1〜8之光資訊記錄媒體。 例如,比較例1是將1 g下述比較化合物(Α)添加溶 解於100 ml 2,2,3,3-四氟丙醇中,製備含有染料的塗佈液。 除此以外,以與上述實施例1〜10同樣的方法製作比較例 1之光資訊記錄媒體。此後的比較例2〜8亦分別使用1 g 下述比較化台物(B)〜(Η),除此以外與比較例1同樣。 比較化合物(Α):日本專利特開2001 — 158862號公 報範疇的化合物In a 50 ml eggplant-shaped flask, 300 mg of the compound (M-1) and 1 ml of decyl alcohol were added: while adding 200 mg of the compound (3) in 5 ml of the alcohol and 5 ml of the distilled water The solution is heated to reflux 1 small 72 200817477 25795pif.doc. After adding 20 ml of distilled water, it was returned to room temperature, and the precipitate was filtered. • Wash with distilled water and dry to obtain 270 mg of compound (M-^). The identification of the compounds was confirmed by the MALDI_MS method. m/z two 762 (nega), 297 (p0si). The various cation-containing azo metal complex dyes of the present invention can be synthesized by the same method as the synthesis of the above compound (M-6). Anion exchange is carried out according to the synthesis method of the compound (M-6), and (;: an azo metal complex containing an organic anion such as (M-18) can be obtained. [Synthesis of Comparative Compound (c)] Comparative Compound ( C): Compound of the Japanese Patent Laid-Open No. 2006-142789. In a 50 ml eggplant-shaped flask, 100 mg of the compound (a-3) and 3 ml of decyl alcohol were added, and while stirring, 34 mg of NiCl2.6H20 was added and stirred for 30 minutes. After entering 20 ml of steamed water, the resulting sediments were filtered, washed with steaming water, and dried to obtain Π0 mg of the comparative compound (C). The compound was confirmed by MALDI-MS. /z=763.5 (p0si) v [Production of optical information recording medium] (Production of substrate 12) I has a thickness of 1.1 mm, an outer diameter of 120 mm, an inner diameter of 15 rnm, and a spiral pre-grooving groove 34. (Extrusion molding made of polycarbonate resin with a distance of 320 nm, groove width, concave _ 4 〇 (recess) width 190 nm, groove depth: 47 nm, groove inclination angle: 65, swing: 20 nm) The mastering of the master (stamper) used for injection molding is utilized. Laser cutting (351 nm) 73 200817477 25795pif.doc (Formation of light-reflecting layer 18) Using a Cube manufactured by Unaxis, on the substrate 12 by DC in an & Forming a film thickness of 6 〇 nm as a direct-air film-forming acoustic ANC light-reflecting layer (Ag: (10) at%, Nd: 〇7 娜, & : 〇9 ^ ). Adjusting the light-reflecting layer 18 by sputtering time Film thickness (formation of recordable recording layer 14) Examples 1 to 10: Compounds 16), (M-17), (M-22), (M-23), (m-26), (m) -%), (]\^—2), (]\4~38) Each 18 is added and dissolved in 1〇〇11,12,2,3,3_tetrafluoropropanol to prepare a coating liquid containing a dye. The prepared dye-containing coating liquid was applied onto the light-reflecting layer 18 under the conditions of 23 ° C and 50% RH by spin coating, while changing the number of revolutions from 500 rpm to 2200 rpm. To form the recordable recording layer 14. After the recordable recording layer 14 is formed, an annealing process is performed in a dean oven, which is formed by separating the spacers on the vertical stacked columns while Substrate 12 is supported Hold at 1 〇 cc for 1 hour. (Formation of barrier layer 2 )) Subsequently, using a Cube manufactured by Unaxis, an Nb2 形成 was formed on the recordable recording layer 14 by DC sputtering in an Ar gas atmosphere. 5 constitutes a barrier layer 20 having a thickness of 10 nm. (Finishing of the cover layer 16) The cover layer 16 is made of polycarbonate having an inner diameter of 15 mm, an outer diameter of 120 mm, and 74 200817477 257y5pif.doc having an adhesive layer on one side (glass transition temperature _26t) Film (TeijinPUREACE, thickness: 80 μm), and the adhesion layer = the total thickness of the polycarbonate film is set to 100 μm, and then on the barrier layer 20, the barrier layer 20 and the adhesive layer The cover layer is placed in abutting manner. The cover layer is then pressed to be crimped and attached to the member. By the above steps, the optical information recording medium 10A having the layer structure shown in Fig. 制作 is produced. Thus, the optical information recording media of Examples 1 to 10 were produced. (Comparative Examples 1 to 8) The production of the optical information recording medium was carried out in the same manner except that the comparative compound (Α) to (Η) was used instead of the exemplary compound (Μ-1) as the dye used in the recordable recording layer 14. Methods The optical information recording media of Comparative Examples 1 to 8 were produced. For example, in Comparative Example 1, 1 g of the following comparative compound (Α) was dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a coating liquid containing a dye. An optical information recording medium of Comparative Example 1 was produced in the same manner as in the above Examples 1 to 10 except for the above. The comparative examples 2 to 8 which have been used in the following are the same as Comparative Example 1 except that 1 g of the following comparative compounds (B) to (Η) are used. Comparative compound (Α): Compound of the Japanese Patent Laid-Open No. 2001-158862
比較化合物(Β):日本專利特開2〇〇1 — 158862號公 報記載的化合物 75 200817477 25795pif.docComparative compound (Β): Compounds described in Japanese Patent Laid-Open Publication No. 2〇〇1 — 158862 75 200817477 25795pif.doc
比較化合物(C):日本專利特開2006 — 142789號公 報範_的化合物Comparative Compound (C): Compound of Japanese Patent Laid-Open No. 2006-142789
Ni2+Ni2+
比較化合物(D):日本專利特開2001 — 306070號公 報記載的化合物Comparative compound (D): a compound described in Japanese Patent Laid-Open Publication No. 2001-306070
比較化A物(E):日本專利特開2005 — 297406號公 報記載的化合物Comparative A substance (E): a compound described in Japanese Patent Laid-Open Publication No. 2005-297406
76 200817477 25795pif.doc 報範疇的化合物76 200817477 25795pif.doc Reporting compounds
Ni2+Ni2+
比幸U (G广日本專利特開謂5 —撕娜號公 報以&本專,2974〇7號練^ / 0"N= C4H9 ^ ^ \ 0^-Ν=Ν^Κ \ NC CH3 n〇2 比較化合物(Η):日本專利特開2000一 168237號公 報記載的化合物Than fortunate U (G Guang Japanese Patent Special Open 5 - Torn No. Gazette & This special, 2974 〇 7 exercises ^ / 0" N = C4H9 ^ ^ \ 0^-Ν=Ν^Κ \ NC CH3 n 〇2 Comparative compound (Η): a compound described in JP-A-2000-168237
(1 ) C/N (載波雜訊比,carrier to noise ratio)評價 對於所製作的光資訊記錄媒體,使用具有403 nm雷 射、NA (數值孔徑)為0.85的讀取頭(pickup)的記錄再 生評價機(PULSTEC公司製:DDU1000),以時鐘頻率 (clock frequency) 66 MHz、線速 4.92 m/s 來記錄及再生 77 200817477 25795pif.doc (U^m的錢(π),#光譜 (Rohde-Schwarz 公司製 Fsp— - C spectrum analyser ) 記錄後的16 MHz的‘作為】:),記錄訊坑再生。將 錄前的16 MHz的輸出作為雜 ( Carner)輸出,將記 的輸出/記錄前的輸出作為C/n信〇ise)輸出,將圯錄後 實施形態之光•記錄方法,記錄^外,本評價時採用本 記錄功率為5 mW〜6 mW,再=凹槽上進订。另外, 於表4。成為記錄特性的指桿^力率為mW。結果示 記錄功率則其值變大的傾向、比,有若增強 靈敏度雙方之觀點而言,奸_⑽比與記錄 後的)下若C/N大於等於35曰犯錄功率5〜6mW (記錄 ^ ^ 、、 ,則記錄靈敏度以及再生 佗唬強度均為充分,記錄特性較好。 (2)染料膜的耐光性評價 冷佈ί備ΪΙΓΓ〜1G、比較例1〜8同樣的含有染料的 二ΐ: ΐ 一邊使旋轉數自500 rpm謂0 _ 内^化’ -邊於23t、50%RH的條件下在厚度u麵的 _板上塗佈所製備的含有染料的塗佈液。隨後,於 2.3C、5G%RH的條件下保存24時間,隨後用旋轉木馬 y merry-go-round)型耐光試驗機(Eagle Engineering 公司 製’ CellTest機皿型’附有Sch〇tt製WG32〇濾光片)進行 耐光性試驗。對㈣紐試驗前的染繼錢_光性試驗 48小時後的染料膜,使用UV-1600PC (SHIMADZU公 司製)測定染料膜的吸收光譜,並讀取最大吸收波長處的 吸光度的變化。作為光資訊記錄媒體用染料,就記錄資訊 78 200817477 2S795pif.doc ^長曰期,存之觀點而言,要求具有極高的 _,疋指若大於等於85% 實 / 。本試驗 表4 …衫分,耐光性較好。 對應的通式 1偶氮金屬錯 合物染料 通式(2〜1) (M — 1) 通式(B) (M-13) 通式(B) (M-16) 通式(B) (M —17) 通式(B) (M—22) 通式(B) (M—23) 通式(3 — 1) (Μ—26 ) 通式(B) (Μ — 32) 通式(2 — 1) (Μ—2) 一(Μ-38) 化合物(Α) 化合物(Β) 化合物(C) 化合物(D) 化合物(Ε) 化合物(F) 化合物(G) 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 記錄再生特性(1) C/N (carrier to noise ratio) evaluation For the optical information recording medium to be produced, a record having a 403 nm laser and a pickup with a NA (numerical aperture) of 0.85 was used. Regeneration evaluation machine (made by PULSTEC: DDU1000), recorded and reproduced at a clock frequency of 66 MHz and a line speed of 4.92 m/s. 77 200817477 25795pif.doc (U^m's money (π), #spectrum (Rohde) - Schwarz company Fsp - - C spectrum analyser ) Recorded 16 MHz 'as':), recording pit regeneration. The 16 MHz output before the recording is used as the Carner output, and the output before the recording/recording is output as C/n signal, and the light and recording method of the embodiment is recorded and recorded. In this evaluation, the power of this recording is 5 mW~6 mW, and then the groove is ordered. In addition, in Table 4. The finger force that becomes the recording characteristic is mW. As a result, the recording power has a tendency to increase in value, and there is a tendency to increase the sensitivity. If the _(10) ratio and the post-recording are lower, the C/N is greater than or equal to 35 曰 the recording power is 5 to 6 mW (recording) ^ ^ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ΐ: ΐ The prepared dye-containing coating liquid was applied to the thickness u-faced plate under the condition of 23t and 50% RH while rotating the number from 500 rpm to 0 _. Stored under conditions of 2.3C and 5G% RH for 24 hours, followed by a rotary trojan y merry-go-round type light resistance tester ("CellTest machine type" manufactured by Eagle Engineering Co., Ltd. with WG32 〇 filter by Sch〇tt Tablet) The light resistance test was carried out. For the dye film after the test for 48 hours, the absorption spectrum of the dye film was measured using UV-1600PC (manufactured by SHIMADZU Co., Ltd.), and the change in absorbance at the maximum absorption wavelength was read. As a dye for optical information recording media, it records information. 78 200817477 2S795pif.doc ^ In the long period of time, it is required to have a very high _, if the finger is greater than or equal to 85% real /. This test has a good light fastness. Corresponding formula 1 azo metal complex dyes of formula (2~1) (M-1) formula (B) (M-13) formula (B) (M-16) formula (B) ( M — 17) Formula (B) (M—22) Formula (B) (M—23) Formula (3—1) (Μ—26) Formula (B) (Μ — 32) Formula (2) — 1) (Μ—2) One (Μ-38) Compound (Α) Compound (Β) Compound (C) Compound (D) Compound (Ε) Compound (F) Compound (G) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Recording and reproducing characteristics
Slljmc/N) 〇 ◎ 本發明 ◎ ◎ ◎ ◎ 〇 ◎ 〇 〇 (註3) 比較例 (註1 )Xe光照射48小^ 存率為大於等於·時為◎,切f於 ς = 〇,大於等於75%小於85%時為△,小於75%時為;^為 贫($ 2) 2T _ C/N為大於等於39 dB時為◎,大於Slljmc/N) 〇 ◎ ◎ ◎ ◎ ◎ 〇 〇〇 注 (Note 3) Comparative example (Note 1) Xe light irradiation 48 small ^ When the ratio is greater than or equal to · when ◎, cut f ς = 〇, greater than When it is equal to 75% less than 85%, it is △, when it is less than 75%; ^ is lean ($ 2) 2T _ C/N is ◎ or more when it is 39 dB or more, larger than
日ί =5册2 39犯時為〇’大於等於·小於35 dB 日守為△,小於30 dB時為X。 故無法 (註3)因溶解性差無法充分地形成記錄層, 進行測定或記錄。 如表4所不,與使用先前的偶氣金屬錯合物的比較例 1〜8相比’右使用貫施例的偶氣染料,則任一染料 79 200817477 257Wpii.doc 艇的耐光性均為良好, 塗佈;對 進而,與實施例的化合物相 』艮好Day ί = 5 volumes 2 39 is 〇' greater than or equal to less than 35 dB. The daily stagnation is △, and when it is less than 30 dB, it is X. Therefore, it is impossible (Note 3) that the recording layer cannot be sufficiently formed due to poor solubility, and measurement or recording is performed. As shown in Table 4, compared with Comparative Examples 1 to 8 using the previous azo metal complex, the light resistance of any dye 79 200817477 257 Wpii.doc was used for the right-handed odor dye. Good, coated; and, in turn, better with the compounds of the examples
的偶氮金屬錯合物染料對涂你—勺认本λ苑形態之實施例 〈染料溶㈣耐紐評2 液敎性較好。 達到屬錯)合物㈣,以吸光度 進行耐光·愤。其結果,任—騎;料 = ==_切祕9Q%。作為’ 要求的重要性能,可舉出耐紐,因此可知於膜、 =中的任—狀態下耐光性均為優異的本發明之化合物, /墨、彩色濾光片、顏色轉換濾光片、照相用材料、熱 軲移^錄材料等各種用途中顯示較好的性能。 進而,將經旋塗於玻璃板上的化合物(M—13)於溫 度8〇p、相對濕度85%的環境中保存24小時,進行同= 定(加溫、加濕實驗)。由其結果可知,未引起吸收光 ϋ曰曼化’高溫南濕度下的保存性優異。 進而可知,本發明之染料於粉末狀態以及膜狀態下, Ρ使於150 C的溫度條件下亦不會分解,熱穩定性優異。 由此可知,本發明之化合物不僅在光資訊記錄媒體中而且 200817477 25795pif.doc 在油墨、彩色濾光片、顏色轉換濾光片、照相用材料等各 種用途中均顯示較好的性能。 另外,本發明之光資訊記錄媒體以及偶氮金屬錯合物 染料並不限定於上述實施形態,在不脫離本發明之要點的 範圍内,當然可採用各種構成。 【圖式簡單說明】 圖1為表示態樣(1)之光資訊記錄媒體的一例的概略 剖面圖。 圖2為表示態樣(2)之光資訊記錄媒體的一例的概略 剖面圖。 【主要元件符號說明】 10A、10B ··光資訊記錄媒體 12、24 :基板 14、26 :可錄式記錄層 16 :覆蓋層 18、30 :光反射層 20 :阻障層 22 :接著層或黏著層 28 :保護基板 32 :接著層 34、36 :預刻溝槽 38 :溝軌 40 :凹槽 42 :第1物鏡 81 200817477The azo metal complex dyes are applied to the formula of the λ Court. The dye solution (4) is resistant to New Zealand. Achieve the wrong compound (4), and absorb light and anger with absorbance. As a result, Ren-riding; material ===_cutting 9Q%. The important performance required for the product is Nike, and it is known that the compound of the present invention, which is excellent in light resistance in any of the films and =, is an ink, a color filter, a color conversion filter, Good performance is exhibited in various applications such as photographic materials, thermal recording materials, and the like. Further, the compound (M-13) spin-coated on the glass plate was stored in an environment of a temperature of 8 〇p and a relative humidity of 85% for 24 hours, and the same was carried out (heating and humidification test). As a result, it was found that absorption light was not caused to be smothered. Further, it is understood that the dye of the present invention does not decompose under a temperature condition of 150 C in a powder state or a film state, and is excellent in thermal stability. From this, it is understood that the compound of the present invention exhibits better performance in various applications such as inks, color filters, color conversion filters, and photographic materials, not only in optical information recording media but also in various applications such as inks, color filters, color conversion filters, and photographic materials. Further, the optical information recording medium and the azo metal complex dye of the present invention are not limited to the above-described embodiments, and various configurations can of course be employed without departing from the gist of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of an optical information recording medium of the aspect (1). Fig. 2 is a schematic cross-sectional view showing an example of an optical information recording medium of the aspect (2). [Main component symbol description] 10A, 10B · Optical information recording medium 12, 24: Substrate 14, 26: Recordable recording layer 16: Cover layer 18, 30: Light reflecting layer 20: Barrier layer 22: Adhesive layer or Adhesive layer 28: protective substrate 32: adhesive layer 34, 36: pre-groove groove 38: groove track 40: groove 42: first objective lens 81 200817477
2!)/yi)plt.d〇C 44 : 46 : 48 : 硬化層 雷射光 第2物鏡2!)/yi)plt.d〇C 44 : 46 : 48 : hardened layer laser light second objective lens
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JP (1) | JP5139989B2 (en) |
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TWI466953B (en) * | 2008-09-25 | 2015-01-01 | Fujifilm Corp | Method for fabricating azo metal complex dye |
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JP2009009684A (en) * | 2007-06-01 | 2009-01-15 | Fujifilm Corp | Optical information recording medium and information recording method |
JP5133284B2 (en) * | 2008-09-25 | 2013-01-30 | 富士フイルム株式会社 | Optical information recording medium, information recording method, and azo metal complex dye |
WO2010041470A1 (en) * | 2008-10-10 | 2010-04-15 | 富士フイルム株式会社 | Optical information recording medium, information recording method and photosensitizer |
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JPS5482385A (en) * | 1977-12-14 | 1979-06-30 | Fuji Photo Film Co Ltd | Stabilizing method for organic basic substance to light |
JPS58175693A (en) | 1982-04-08 | 1983-10-14 | Ricoh Co Ltd | High density optical information recording medium |
US5145963A (en) * | 1988-10-12 | 1992-09-08 | Ricoh Company, Ltd. | Optical information recording medium and nickel dithiolate complex compounds employed in the same |
US5633106A (en) * | 1994-04-08 | 1997-05-27 | Mitsui Toatsu Chemicals, Inc. | Optical recording media and a method of recording and reproducing information |
JPH11130970A (en) | 1997-10-31 | 1999-05-18 | Mitsubishi Chemical Corp | Metal-containing azo compound and optical recording medium prepared by using same |
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JP2000168237A (en) | 1998-12-07 | 2000-06-20 | Tdk Corp | Optical recording medium |
JP2001158862A (en) | 1999-12-02 | 2001-06-12 | Mitsubishi Chemicals Corp | Metal chelate coloring matter and optical recording medium |
JP4666742B2 (en) * | 1999-12-14 | 2011-04-06 | 株式会社林原生物化学研究所 | Light absorbers and their applications |
JP4119099B2 (en) | 2001-03-21 | 2008-07-16 | 株式会社リコー | Optical recording medium |
JP2004209771A (en) * | 2002-12-27 | 2004-07-29 | Fuji Photo Film Co Ltd | Optical information recording medium |
JP2005074852A (en) * | 2003-09-01 | 2005-03-24 | Mitsui Chemicals Inc | Optical recording medium using monomethine complex compound |
JP2005162812A (en) | 2003-12-01 | 2005-06-23 | Konica Minolta Holdings Inc | Colored composition, inkjet recording ink, color toner, optical recording medium, ink sheet for thermally sensitive transfer recording material, color filter, and inkjet recording method using the inkjet recording ink |
JP4482701B2 (en) * | 2004-04-13 | 2010-06-16 | 株式会社東芝 | Write-once information recording medium |
JP2005297406A (en) * | 2004-04-13 | 2005-10-27 | Toshiba Corp | Recording material for medium |
JP4552638B2 (en) * | 2004-10-20 | 2010-09-29 | コニカミノルタホールディングス株式会社 | Optical information recording medium and information recording method |
TW200634099A (en) | 2004-12-08 | 2006-10-01 | Clariant Int Ltd | Pyridine n-oxide based azo dyes and their metal complexes for use in optical layers for optical data recording |
JP4519795B2 (en) | 2005-03-29 | 2010-08-04 | 三菱化学メディア株式会社 | Optical recording medium and metal complex compound |
CN101238182B (en) * | 2005-07-14 | 2013-09-11 | 三菱化学媒体株式会社 | Optical recording medium, optical recording material and metal complex compound |
JP2007175968A (en) | 2005-12-27 | 2007-07-12 | Fujifilm Corp | Optical recording medium |
JP2009262338A (en) * | 2008-04-22 | 2009-11-12 | Fujifilm Corp | Optical information recording medium, information recording/reproduction method and new phthalocyanine derivative |
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2007
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TWI466953B (en) * | 2008-09-25 | 2015-01-01 | Fujifilm Corp | Method for fabricating azo metal complex dye |
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JPWO2008038765A1 (en) | 2010-01-28 |
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